UC-NRLF 


METHODS 


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REESE  LIBRARY 

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UNIVERSITY  OF  CALIFORNIA 

-TfcY.  J^6.  ,  /Sn^. 

^r  7.. 

Accession  No.  ///    .7/6    .Class  No. 


I, 


METHODS  FOR  THE  ANALYSIS 


OF- 


Ores,  Pig  Iron  and  Steel 


IN  USE;  AT  THE; 


Laboratories  of  Iron  and  Steel  Works 


-IN  THE;- 


REGION  ABOUT  PITTSBURG,  PA. 


TOGETHER  WITH  AN  APPENDIX   CONTAINING  VARIOUS 

SPECIAL  METHODS  OF  ANALYSIS  OF  ORES 

AND  FURNACE  PRODUCTS. 


CONTRIBUTED  BY  THE 

CHEMISTS  IN   CHARGE,  AND  EDITED  BY  A  COMMITTEE  OF 

THE  CHEMICAL,  SECTION,  ENGINEERS'  SOCIETY 

OF  WESTERN  PENNSYLVANIA. 


UNIVERSITY  j 


EASTON,  PA. 
CHEMICAL  PUBLISHING  Co. 

1898. 


PREFACE. 


These  methods  in  use  in  the  iron  and  steel  laboratories  of  the 
region  near  Pittsburg,  Pa.,  were  collected  and  published  by  the 
Engineers  Society  of  Western  Pennsylvania  during  1896.  The 
supply  of  copies  having  been  exhausted,  in  response  to  a  contin- 
uous demand  the  publication  in  more  convenient  form  has  been 
undertaken  by  the  Chemical  Publishing  Company  who  have  been 
authorized  to  do  so  by  resolution  of  the  Society  at  a  meeting 
held  March  13,  1897. 

These  methods  were  detailed  by  those  using  them  in  response 
to  the  following  circular  sent  out  by  the  committee  in  charge : 

CHEMICAL  SECTION. 

ENGINEERS'  SOCIETY  OF  WESTERN  PENNSYLVANIA, 
PITTSBURG,  PA. 

In  accordance  with  a  resolution  of  the  Chemical  Section  of  the  Engi- 
neers Society  of  Western  Pennsylvania,  the  undersigned  wish  to  ask  your 
cooperation  in  an  effort  to  collect,  for  publication  in  the  Proceedings  of 
the  Society,  the  method  of  analysis  in  use  in  the  various  iron  and  steel 
works  laboratories  of  the  region. 

In  calling  the  attention  of  chemists  to  the  plan  and  asking  their  aid  in 
its  fulfilment,  it  should  be  mentioned  that  it  is  the  aim  of  the  Section  to 
secure  accurate  statements  of  analytical  processes,  describing  with  minute- 
ness and  clearness  the  successive  steps,  in  order  that  the  proposed 
compilation  may  represent  as  correctly  as  possible  the  present  status  of 
analytical  chemistry  as  applied  to  iron  and  steel. 

A  full  presentation  of  the  methods  in  general  use  is  likely  to  prove  of 
interest  and  value,  but  the  completeness  and  promptness  of  the  responses 
received  from  a  large  number  of  chemists  must  determine  the  success  of 
the  measure. 

In  case  you  are  willing  to  cooperate,  you  are  requested  to  send  to  any 
one  of  the  undersigned  a  full  description  of  the  methods  you  use  for  the 
determination  of  the  following  substances  : 

In  Ores — Silica,  iron,  phosphorus,  manganese. 

In  Pig  Iron — Silicon,  sulphur,  phosphorus,  manganese. 

In  Steel — Carbon  (by  combustion),  sulphur,  phosphorus,  manganese, 
nickel. 

SUGGESTIONS  \ 

i.  If  the  method  is  described  in  a  text-book  or  journal,  a  mere  reference 


iv  Preface. 

will  suffice,  but  any  deviations  from   the  published  methods    should  be 
noted. 

2.  In  writing  a  description  of  a  method  it  is  very  desirable  that  minute 
details  should  be  given  (e.  g.,  weights  taken,  volume  of  solution,  temper- 
atures, etc.,  etc.). 

3.  If  more  than  one  method  is  used,  please  describe  the  one  in  every- 
day use  on  which  the  commercial  transactions  of  the  firm  are  based. 

4.  It  is  earnestly  requested  that  a  reply  be  sent  at  the  earliest  possible 
date. 

Bach  method  will  be  published  over  the  name  of  the  sender.  The  work 
of  the  committee  will  be  confined  to  collecting  and  arranging  for  publi- 
cation without  comment  or  discussion. 

F.  C.  PHILIPS, 

Western  University,  Allegheny,  Pa. 
A.  G.  McKBNNA, 

Duquesne  Steel  Works,  Duquesne,  Pa. 
E.  S.  JOHNSON, 

Park  Bros.  &  Co.,  Pittsburg,  Pa. 

Committee. 

The  methods  which  have  been  received  in  response  to  this 
circular  may  be  considered  to  represent  the  general  practice  of 
the  chief  iron  and  steel  works  in  the  region  of  Pittsburg  and 
Western  Pennsylvania. 


CONTENTS. 

I. — Methods  used  at  the  Laboratory  of  the  Carnegie  Steel  Co.,  Home- 
stead, Pa.     By  John  S.  Unger i 

II. — Methods  used  at  the  Laboratory  of  the  Monongahela  Furnace, 

McKeesport,  Pa.     By  Frederick  Crabtree 12 

III. — Methods  used  at  the  Laboratory  of  the  Junction  Iron  and  Steel 

Co.,  Steubenville,  Ohio.     By  Joseph  M.  Wilson 16 

IV. — Methods  used  at  the  Laboratory  of  the  Carnegie  Steel  Co.,  Lucy 

Furnace,  Pittsburg,  Pa 21 

V. — Methods  used  at  the  Laboratory  of  the  Black  Diamond  Steel 

Works,  Pittsburg,  Pa.     By  Edward  S.Johnson 23 

VI. — Methods  used  at  the  Laboratory  of  the  Oliver  and  Snyder  Steel 

Works,  Pittsburg,  Pa.     By  S.  M.  Rodgers 36 

VII. — Methods  used  at  the  Laboratory  of  the  Hainsworth  Steel  Co., 

Edith  Furnace  Dep't,  Allegheny,  Pa.     By  R.  G.  Johnston 47 

VIII.— Methods  used  at  the  Laboratory  of  the  Carnegie  Steel  Co., 

Edgar  Thomson  Steel  Works  and  Furnaces,  Braddock,  Pa.    By 

C.  B.  Murray 50 

IX. — Methods  used  at  the  Laboratory  of  the  Clinton  Iron  and  Steel 

Co.,  Pittsburg,  Pa.     By  A.  B.  Harrison 57 

X. — Methods  used  at  the  Laboratory  of  the  Isabella  Furnace  Co., 

Etna,  Pa.     By  F.  G.  Brinker 60 

XI. — Methods  used  at  the  Laboratory  of  the  Shenango  Valley  Steel 

Co.,  New  Castle,  Pa.     By  Warren  R.  Clifton 63 

XII. — Methods  used  at  the  Laboratory  of  the  Pennsylvania  Railroad 

Co.,  Altoona,  Pa.     By  C.  B.  Dudley  and  F.  N.  Pease 70 

XIII.— Methods  used  at  the  Laboratory  of  Mclntosh,  Hemphill  &  Co., 

Pittsburg,  Pa.     By  J.  P.  McKelvey 72 

XIV.— Methods  used  at  the  Laboratory  of  the  W.  Dewees  Wood  Co., 

McKeesport,  Pa.     By  Theo.  Tonnele  and  R.  B.  Carnahan,  Jr..     74 
XV.— Methods  used  at  the  Laboratory  of  the  Ohio  Steel  Co.,  Youngs- 
town,  Ohio.     By  J.  C.  Barrett 80 

XVI. — Methods  used  at  the  Laboratory  of  the  Carnegie  Steel  Co., 

Duquesne,  Pa.     By  James  M.  Camp 88 

APPENDIX. 

Blast-furnace  Cinders  and  their  Analysis.     By  James  M.  Camp 101 

Barium  Hydroxide  as  an  Absorbent  in  Carbon  Determinations.    By  A. 

G.  McKenna 109 

An  Improvement  in  the  Zinc  Reductor  for  the  Determination  of  Iron 

or  Phosphorus.     By  A.  G,  McKenna 113 

On  Some  Evolution  Methods  for  Sulphur  in  Iron  and  Steel.     By  W. 

E.  Garrigues 117 

The  Determination  of  Chromium.     By  A.  G.  McKenna 121 

Notes  on  the  Analysis  of  Mill  and  Puddle  Cinders.   By  Jos.  M.  Wilson  124 
The  Complete  Analysis  of  Chrome  Ore.     By  A.  G.  McKenna 129 


OF   THF 

UN'  VTY 


I.  METHODS  USED  AT  THE   LABORATORY  OF  THE 
CARNEGIE  STEEL  CO.,  HOMESTEAD,  PA. 

BY  JOHN  S.  UNGER. 


DETERMINATION  OF  SIUCA  IN  ORES  OF  IRON  AND  MANGANESE. 

To  i  gram  of  the  ground  ore  in  an  8-oz.  beaker  add  35  cc.  of 
hydrochloric  acid  (sp.  gr.  1.20),  cover  with  a  watch-glass,  and 
boil  gently  on  a  hot  plate  for  twenty  minutes.  Remove  and 
rinse  watch-glass  and  sides  of  beaker  with  15  cc.  of  water,  filter 
off  insoluble  matter  on  an  n-cm.  filter,  catching  filtrate  in  an  8- 
oz.  beaker,  and  wash  with  water  until  soluble  matter  is  removed. 
The  filtrate,  which  should  not  exceed  90  cc.,  is  placed  on  a  sand- 
bath  and  allowed  to  go  to  dryness.  The  filter  is  ignited  and  the 
residue  fused  with  8  grams  of  sodium  carbonate.  The  fusion  is 
run  up  around  the  sides  of  the  crucible  and  then  the  crucible  is 
cooled  by  dipping  cautiously  in  an  8-oz.  beaker  containing 
35  cc.  water,  finally  turning  the  crucible  on  its  side  and  leaving 
it.  Cover  beaker  with  a  watch-glass  and  add  hydrochloric  acid 
gradually  until  effervescence  ceases.  After  the  fusion  dissolves 
out  of  the  crucible,  remove  with  a  glass  rod  and  wash  the  cruci- 
ble with  water.  The  solution  should  not  exceed  90  cc.  Evap- 
orate on  a  sand-bath  to  dry  ness.  When  both  solutions  are  evap- 
orated, moisten  the  residues  with  10  cc.  hydrochloric  acid 
(sp.  gr.  i. 20)  and  leave  on  the  bath  for  a  few  minutes  ;  then  add 
20  cc.  hot  water,  and  filter  through  an  n-cm.  filter,  the  first 
into  a  i6-pz.  Erlenmeyer  flask,  washing  out  the  beaker  carefully, 
then  filter  the  second  through  the  same  filter.  If  the  alkaline 
salts  have  not  all  dissolved  in  the  second  add  20  cc.  hqt  water 
and  stir  until  dissolved;  filter,  and  rinse  the  beaker  with  hot 
water  until  filter  is  perfectly  free  from  soluble  salts.  Ignite  the 
filter  in  a  muffle,  cool,  and  weigh  as  pure  silica.  The  filtrate, 
which  is  preserved  for  further  use,  should  not  exceed  150  cc. 

DETERMINATION  OF  IRON  IN  IRON    ORES. 

To  the  filtrate  from  silica   (given  under  silica)  add  12  grams 


2  John  S.    Unger. 

of  Baker  and  Adamson's  shot  zinc  and  locc.  concentrated  hydro- 
chloric acid,  and  place  in  the  neck  of  the  flask  a  small  funnel.  Let 
the  flask  stand  for  about  twenty  or  thirty  minutes  or  until  the  iron 
is  all  reduced,  Should  the  action  on  the  zinc  become  feeble,  add 
10  cc.  concentrated  hydrochloric  acid.  When  the  iron  is  re- 
duced test  a  drop  of  the  solution  with  a  drop  of  potassium  thio- 
cyanate  on  a  white  porcelain  plate. .  If  it  shows  no  color  or  just 
a  very  faint  pink,  it  is  ready  for  titration.  Have  ready  a  i6-oz. 
wide  beaker,  a  platinum  triangle  large  enough  to  extend  over 
the  edges  of  the  beaker,  and  a  Gooch  crucible  with  a  tuft  of  glass 
wool  \  inch  thick  at  the  bottom.  Rinse  the  funnel  into  the  flask 
with  a  wash-bottle  and  pour  the  solution  through  the  Gooch 
crucible,  receiving  the  solution  in  the  beaker.  Rinse  the  flask 
three  times  with  about  10  or  15  cc.  of  water  and  wash  the  Gooch 
crucible  once.  To  the  filtrate  in  the  beaker  add  5  cc.  concen- 
trated hydrochloric  acid  and  place  on  a  hot  plate  for  two  minutes. 
The  solution  will  now  occupy  225  cc.  Remove  from  the  heat 
and  titrate  with  standard  bichromate  solution,  using  3  drops  for 
each  test  toward  the  end,  and  adding  the  bichromate  solution, 
5  drops  at  a  time,  when  almost  done.  Agitate  each  test  drop 
by  blowing  gently,  and  continue  the  addition  of  the  bichromate 
until  the  last  test  shows  an  absence  of  blue  precipitate  after 
agitating  and  standing  thirty  seconds.  The  bichromate  used, 
multiplied  by  the  factor,  gives  the  metallic  iron. 

The  potassium  thiocyanate  solution  is  made  by  dissolving  10 
grams  of  the  salt  in  100  cc.  water  and  is  kept  in  a  small  bottle 
provided  with  a  glass  cap  and  a  short  piece  of  -|~inch  glass  tu- 
bing to  be  used  as  a  pipette  in  taking  out  the  test  drops.  The 
potassium  ferricyanide  solution  is  made  by  dissolving  i  gram  of 
the  salt  in  100  cc.  water  and  test  drops  are  removed  as  with  thio- 
cyanate. The  solution  must  be  made  up  each  day.  One  drop 
is  used  for  a  test. 

The  potassium  bichromate  is  made  by  dissolving  52  grams  in 
12  liters  of  water,  then  shaking  well  and  keeping  the  stock  bottle 
protected  from  light. 

The  porcelain  plate  is  6  by  6  inches  with  1 2  depressions  i  inch 
wide  by  \  inch  deep  on  its  surface. 

The  bichromate  solution  is  standardized  by  dissolving  3  por- 


Carnegie  Steel  Company,  Homestead,  Pa.  3 

tionsofabouto.3gram,o.5gram,  and  0.7  gram,  respectively,  of  per- 
fectly clean,  soft,  iron  wire  of  99.80  per  cent,  pure  iron  in  a  i6-oz. 
Brlenmeyer  flask  (having  a  small  funnel  in  the  neck),  in  40  cc. 
dilute  hydrochloric  acid,  by  the  aid  of  gentle  heat.  When  dis- 
solved, rinse  the  funnel  and  sides  of  flask  and  make  the  solution  up 
to  150  cc.  Add  12  grams  of  zinc  and  when  the  iron  is  reduced, 
titrate  exactly  as  in  case  of  iron  in  ore.  The  weight  of  the  wire 
taken,  multiplied  by  0.998  and  divided  by  the  number  of  cubic 
centimeters  of  bichromate  solution  used,  gives  the  factor  and 
these  factors  should  agree  to  the  third  decimal  place. 

For  iron  in  manganese  ores,  the  basic  acetate  precipitate  of 
iron  spoken  of  under  manganese  is  dissolved  in  40  cc.  dilute 
hydrochloric  acid,  the  solution  made  up  to  150  cc.  and  treated 
exactly  as  in  the  case  of  the  determination  of  iron  in  iron  ores. 

DETERMINATION  OF  PHOSPHORUS  IN  STEEL,  PIG  IRON,  AND  ORES. 

Dissolve  1.63  grams  of  steel  in  a  6-oz.  Krlenmeyer  flask  in  30 
cc.  nitric  acid  (sp.  gr.  1.20).  Place  the  flask  over  a  burner  and 
evaporate  over  a  naked  flame  to  15  cc. ,  add  to  the  boiling  solution 
20  cc.  chromic  acid  solution,  and  again  evaporate  to  18  cc.,  re- 
move from  fire  and  wash  down  the  sides  of  the  flask  with  from  5  to 
7  cc.  water  and  cool  to 40° or  45°  C.  Add6occ.  molybdate  solution, 
previously  filtered  and  heated  to  40°  or  45°  C.,  insert  a  stopper  in 
the  flask,  and  shake  for  five  minutes.  Leave  stand  in  a  warm  place 
for  fifteen  minutes,  then  filter  through  a  7-cm.  (Baker  and 
Adamson,  A  grade)  filter,  previously  dried  and  weighed  at 
110°  C.,  and  wash  with  a  2  per  cent,  nitric  acid  solution  until 
free  from  iron,  then  twice  with  95  per  cent,  alcohol.  Dry 
twenty  minutes  at  110°  C.  and  weigh.  Each  milligram  corre- 
sponds to  o.ooi  per  cent,  phosphorus. 

In  case  of  pig  iron  dissolve  1.63  grams,  in  a  4|-inch  evaporating 
dish,  in  40  cc.  nitric  acid  (sp.  gr.  1.20),  and  evaporate  to  dry- 
ness  on  a  sand-bath.  Then  place  on  a  burner  and  heat  over  the 
naked  flame  until  the  mass  ceases  to  evolve  red  fumes,  allow 
dish  to  cool  and  add  25  cc.  hydrochloric  acid  (sp.  gr.  1.20). 
Cover  with  a  watch-glass,  and  evaporate  to  10  cc.  Add 
cautiously  25  cc.  nitric  acid  (sp.  gr.  1.42)  and  evaporate  to 
12  cc.,  remove  from  burner,  rinse  the  watch-glass  and  sides  of  dish 


4  John  S.    Unger. 

with  12  cc.  water,  filter  through  an  n-cm.  filter  into  a6-oz.  flask, 
and  wash  with  water.  The  solution  should  not  exceed  50  cc. 
Heat  to  40°  C.,  add  60  cc.  molybdate  solution  previously  filtered 
and  heated  to  40°  or  45°  C.,  shake,  and  finish  as  for  steel. 

In  case  of  manganese  ores  dissolve  1.63  grams  in  40  cc.  hydro- 
chloric acid  (sp.  gr.  1.20)  in  a  4^-inch  evaporating  dish,  by  gentle 
boiling,  then  evaporate  to  dryness  on  a  sand-bath,  add  25  cc.  nitric 
acid  (sp.  gr.  1.42),  and  evaporate  to  12  cc.,  dilute  with  12  cc. 
water,  and  filter  through  an  n-cm.  filter  into  a  6-oz.  flask.  The 
solution  should  not  exceed  50  cc.  Heat  to  40°  or  45°  C.,  pre- 
cipitate, and  finish  as  in  the  case  of  steel. 

In  case  of  iron  ores,  if  no  phosphorus  exists  in  the  insoluble  resi- 
due and  the  ore  is  easily  decomposed,  proceed  exactly  as  for  man- 
ganese ore.  Should  phosphorus  exist  in  the  insoluble  residue, 
dissolve  1.63  grams  in  40  cc.  hydrochloric  acid  (sp.  gr.  1.20)  in 
an  8-oz.  beaker  by  gentle  boiling  for  twenty  minutes,  dilute  with 
20  cc.  water,  and  filter  into  an  8-oz.  beaker,  washing  with  water; 
set  filtrate  on  a  sand-bath  and  evaporate  to  dryness.  Ignite 
residue  and  then  fuse  with  8  grams  of  sodium  carbonate  and 
dissolve  fusion  as  for  iron  in  ore,  evaporate  the  solution  to  dry- 
ness  on  a  sand-bath,  add  to  each  beaker  25  cc.  nitric  acid  (sp.  gr. 
1.42),  and  evaporate  carefully  to  12  cc.;  dilute  with  12  cc. 
water  and  filter  both  through  an  n-crn.  filter  into  an  8-oz.  flask, 
using  the  same  filter  for  both  solutions.  Wash  with  water,  heat 
to  40°  or  45°  C.,  and  proceed  as  for  steel. 

The  chromic  acid  solution  is  made  by  dissolving  30  grams  of 
pure  chromic  acid  in  two  liters  of  nitric  acid  (sp.  gr.  1.42)  at 
a  gentle  heat.  It  must  be  made  up  fresh  at  least  every  two 
weeks. 

The  molybdic  acid  solution  is  made  by  mixing  100  grams 
molybdic  acid  to  a  paste  with  265  cc.  water,  then  adding  155  cc. 
ammonia  (sp.  gr.  0.90)  and  stirring  until  all  is  dissolved.  To  this 
solution  add  66  cc.  nitric  acid  (sp.  gr.  1.42),  stir  and  set  aside 
for  an  hour.  In  another  vessel  make  a  mixture  of  395  cc.  nitric 
acid  (sp.  gr.  1.42)  and  i,ioocc.  water.  Then  pour  the  first 
solution  into  the  second  in  a  small  stream,  stirring  constantly. 
Let  stand  for  twenty-four  hours  when  it  is  ready  for  use. 

The  filter-papers  for  weighing  the  yellow  precipitate  are  Baker 


Carnegie  Steel  Company,  Homestead,  Pa. 


and  Adamson's  y-cm.  A  grade.  These  retain  the  precipitate 
without  its  showing  a  tendency  to  pass  through,  and  do  not  con- 
tain an  appreciable  amount  of  soluble  matter,  which  might  be 
extracted  by  the  acid  solution. 

The  stand  for  the  evaporation  over  the  burners  is  made  of  i- 
inch  angle  iron  bent  and  fitted  with  ^-inch  asbestos  mill  board, 
having  a  2|-inch  hole  over  each  burner ;  this  supports  the  flask 
easily  and  prevents  the  solution  from  baking  on  the  sides. 

The  drying  bath  is  a  copper  drum  with  a  coil  of  i-inch  steam 
pipe  at  bottom  and  fitted  with  a  movable  disk,  near  the  top,  hav- 
ing -J-inch  holes,  through  which  the  stem  of  the  funnel  is  inserted, 
the  whole  being  covered  by  a  lid.  Steam  is  supplied  at  boiler- 
pressure  and  a  temperature  of  110°  C.  with  very  little  fluctuation 
is  constantly  maintained. 

DETERMINATION    OF    MANGANESE    IN    MANGANESE   ORES. 

To  the  filtrate  from  silica  previously  spoken  of,  add  ammonia. 
When  almost  neutral,  add  it  drop  by  drop  until  the  solution 
assumes  a  reddish  brown  color.  When  the  last  drop  produces 
a  reddish  brown  precipitate,  which  does  not  dissolve  on  shaking, 
add  10  to  15  cc.  of  ammonium  acetate  and  bring  to  a  boil.  Boil 
one  minute.  Then  remove  and  let  the  precipitate  settle  ;  filter 
through  a  i2j-cm.  filter,  catching  the  filtrate  in  a  i6-oz.  beaker, 
and  wash  out  the  flask  once  with  hot  water.  When  the  filter  has 
run  dry,  place  a  funnel  in  the  flask,  and  dissolve  precipitate  in  15 
cc.  dilute  hydrochloric  acid  (i  :  i),  wash  iron  out  of  paper,  and 
repeat  the  precipitation  with  ammonia  and  ammonium  acetate, 
combining  the  filtrates.  Wash  the  precipitate  three  times  with 
hot  water  and  reserve  for  the  estimation  of  iron.  To  the  fil- 
trate add  three  drops  of  solution  of  phenol-phthalein,  then 
ammonia  until  pink,  then  3  cc.  in  excess.  Pass  a  current  of 
hydrogen  sulphide  through  the  solution  for  ten  minutes,  rinse 
delivery-tube  and  set  beaker  on  sand-  or  steam-bath  for  thirty 
minutes,  filter  through  a  double-pointed  7-  andii-cm.  filter,  and 
wash  with  dilute  ammonium  sulphide  water.  When  washed 
place  a  clean  i2-oz.  beaker  under  funnel  and  pour  over  precipi- 
tate 40  cc.  of  a  mixture  of  20  cc.  hot  water  and  20  cc.  of  50  per 
cent,  acetic  acid,  keeping  the  funnel  covered  with  a  watch-glass. 


6  John  S.    Unger. 

If  the  manganese  sulphide  does  not  all  dissolve  pour  the  solu- 
tion through  the  filter  again,  wash  filter  four  times  with  hot 
water,  and  place  beaker  on  a  hot  plate.  Boil  for  fifteen  minutes, 
dilute  to  150  cc  ;  add  15  cc.  ammonium  phosphate,  and  if  a  pre- 
cipitate forms,  add  a  few  cc.  of  hydrochloric  acid  until  dissolved, 
bring  to  a  boil,  and  then  precipitate  by  adding  ammonia,  drop  by 
drop,  until  the  solution  smells  of  ammonia.  While  precipitating, 
stir  constantly  to  bring  the  precipitate  down  in  a  granular  form, 
filter  through  a  i2^-cm.  filter,  using  suction,  ignite  in  a  muffle, 
and  weigh  as  manganese  pyrophosphate. 

The  ammonium  acetate  solution  is  made  by  dissolving  120 
grams  in  2,000  cc.  water,  then  filtering. 

The  ammonium  phosphate  is  a  saturated  solution  of  the  salt 
in  cold  water,  diluted  with  an  equal  bulk  of  water. 

DETERMINATION    OF   SILICON    IN    PIG   IRON. 

Weigh  into  a  4^-inch  evaporating  dish  0.9333  gram  of  sam- 
ple, cover  with  a  watch-glass,  then  add  50  cc.  of  a  mixture  of 
10  cc.  sulphuric  acid  (sp.  gr.  1.83)  and  40  cc.  water.  Place  over 
a  Bunsen  burner,  supporting  the  dish  on  a  piece  of  ^-inch  asbes- 
tos board,  having  a  2^-inch  hole  in  the  center,  and  evaporate 
until  dense,  white  fumes  escape,  and  the  drop  of  water  which 
condenses  on  the  watch-glass  falls  back  into  the  dish  with  a 
hissing  sound.  Remove  the  dish  from  the  fire  and  let  cool  for  two  or 
three  minutes.  Then  cautiously  add  50  cc.  of  a  mixture  of  10 
cc.  hydrochloric  acid  (sp.  gr.  1.20)  and  40  cc.  water,  place  over 
burner,  and  bring  to  a  boil.  Boil  gently  for  one  minute,  remove 
from  the  fire,  rinse  the  watch-glass,  and  filter  the  solution  through 
an  1 1 -cm.  filter.  Wash  once  with  water,  then  with  dilute  hydro- 
chloric acid  (t  :  i)  and  finally  with  water  until  free  from  iron. 

Ignite  the  precipitate  in  the  muffle,  cool,  and  weigh.  To  the 
residue  in  the  crucible  add  from  4  to  10  drops  pure  hydrofluoric 
acid,  depending  on  the  amount  of  silica  present.  Drive  off 
excess  of  acid  by  heating  gently  on  a  hot  iron  plate,  then  ignite 
for  two  or  three  minutes  in  a  muffle,  cool,  and  weigh. 

The  difference  in  weight  is  divided  by  2,  and  a  decimal  point 
inserted  two  places  from  the  right  hand  gives  the  percentage  of 
silicon  in  the  sample. 


Carnegie  Steel  Company,  Homestead,  Pa.  7 

DETERMINATION    OF   SULPHUR    IN   PIG   IRON    AND    STEEL. 

Weigh  5  grams  of  the  sample  into  a  i6-oz.  side-necked  flask, 
fitted  with  a  rubber  stopper  and  thistle-tube.  An  8-oz.  beaker 
of  the  tall,  narrow  shape,  containing  15  cc.  of  cadmium  solution 
and  filled  to  within  one  inch  from  the  top  with  water,  is  placed  under 
the  delivery-tube.  Then  90  cc.  of  a  mixture  of  40  cc.  hydro- 
chloric acid  (sp.  gr.  1.20)  and  50  cc.  water,  are  poured  into  the 
thistle-tube  and  the  apparatus  is  placed  on  a  stand  made  of  \- 
inch  asbestos  mill  board,  having  a  2^-inch  hole  at  one  side  and 
heated  by  a  Bunsen  burner.  The  heating  is  so  regulated  that 
the  evolved  gases  are  delivered  at  about  3  bubbles  per  second. 
As  the  action  grows  feeble,  the  heat  is  increased,  until  finally 
when  all  is  dissolved,  the  solution  is  brought  to  a  boil  and  kept 
boiling  for  one  minute.  The  delivery-tube  is  then  raised  out  of 
the  beaker  and  the  flask  set  aside. 

The  contents  of  the  beaker  are  then  poured  into  a  i2-oz.  wide 
beaker,  the  precipitate  is  washed  out  of  the  beaker  with  a  wash- 
bottle,  and  5  cc.  of  starch  paste  are  added.  35  cc.  of  a  mixture  of 
40  cc.  hydrochloric  acid  (sp.  gr.  1.20)  and  50  cc.  water  are  then 
poured  into  the  absorption  beaker  and  rinsed  into  the  solution 
in  the  large  beaker.  The  sulphur  is  then  immediately  titrated 
with  standard  iodine  solution. 

The  iodine  solution  is  made  by  dissolving  8  grams  iodine  and 
30  grams  potassium  iodide  in  200  cc.  cold  water  and  then  dilu- 
ting to  about  1,850  cc.  A  standard  steel  is  then  tested  by  the 
method  and  the  result  noted,  and  from  this  the  amount  of  water 
needed  to  dilute  the  iodine  so  as  to  bring  it  to  the  required 
strength,  is  calculated.  After  diluting,  two  determinations  are 
made  on  the  standard  steel  to  see  that  the  iodine  solution  is 
exactly  right.  The  iodine  solution  is  made  of  such  strength 
that  i  cc.  =  o.oi  per  cent,  of  sulphur  in  the  sample.  Two  liters 
of  standard  iodine  are  made  up  at  once  and  the  solution  is  pre- 
served in  a  dark  cupboard.  The  amount  actually  in  use  is  kept 
in  a  special  burette  having  a  blackened  receiver  to  exclude  light. 
The  stock  solution  is  standardized  every  week. 

The  cadmium  solution  is  made  by  dissolving  300  grams  cad- 
mium chloride  in  i  liter  hot  water  in  a  large  bottle  and  then 
adding  1.5  liters  ammonia  (sp.  gr.  0.90),  filtering  through  a 


8  John  S.    Unger. 

fluted  filter  into  a  1 2-liter  bottle.  6.5  liters  ammonia  (sp.  gr. 
0.90)  are  then  added  to  the  solution  and  3  liters  of  water. 
The  whole  is  well  shaken  when  it  is  ready  for  use. 

The  starch  paste  is  made  by  heating  i  liter  of  water  to  boiling- 
point  in  a  i,2oo-cc.  flask  and  adding  gradually  10  grams  of  starch 
made  into  a  cream  with  50  cc.  cold  water.  Keep  the  solution 
boiling  constantly.  When  all  the  starch  is  added  boil  five 
minutes,  then  set  aside  to  cool,  decant  the  liquid,  throwing  the 
last  50  cc.  away. 

The  solution  is  made  up  every  three  days. 

DETERMINATION   OF   CARBON   IN    STEEL. 

5  grams  of  the  sample  are  weighed  into  a  clean  8-oz.  flask 
and  200  cc.  of  copper  potassium  chloride  added  ;  the  flask  is 
closed  with  a  rubber  stopper  and  shaken  until  the  precipitated 
copper  is  completely  redissolved,  which  is  easily  detected  by  the 
absence  of  copper-covered  particles  at  the  bottom  of  the  flask. 
Remove  and  rinse  the  stopper,  then  filter  through  a  perforated 
platinum  boat,  having  a  layer  of  asbestos  \  inch  thick  at  bottom 
and  held  in  a  platinum  holder.  Wash  the  residue  twice  with 
concentrated  hydrochloric  acid,  then  with  water  until  all  the 
soluble  matter  has  been  removed.  Dry  the  boat  for  two  hours 
at  90°  C.  when  it  is  ready  for  burning.  Introduce  into  the 
combustion-tube,  pushing  it  against  theroll  of  silverfoil,  andstart 
a  current  of  oxygen  from  the  cylinder  through  the  apparatus  at 
2  to  3  bubbles  per  second.  In  the  meantime  weigh  the  potash 
bulb  and  the  small  calcium-chloride  tube  filled  with  solid  potas- 
sium hydroxide.  Attach  the  bulb  and  tube  to  the  apparatus 
and  light  first  two  burners  and  leave  burning  for  five  minutes  to 
heat  platinum  gauze  in  a  combustion-tube  to  redness,  then  light 
the  next  burner  and  leave  burning  two  minutes,  following  this 
by  the  others  in  exactly  the  same  way.  When  all  are  lighted 
leave  burning  five  minutes.  Then  shut  off  the  oxygen  and  start 
the  air  current,  being  careful  to  make  the  change  without  allow- 
ing any  back-pressure  from  the  air  in  the  room.  Aspirate  air 
for  forty  minutes,  using  i  liter,  and  weigh. 

The  copper  potassium  chloride  solution  is  made  by  saturating 
2  liters  of  cold  water  with  the  salt,  adding  to  the  solution  100  cc. 


Carnegie  Steel  Company,  Homestead,  Pa.  9 

of  hydrochloric  acid  (sp.  gr.  1.20),  then  i  gram  of  a  high  car- 
bon steel,  shaking  until  dissolved,  then  filtering  the  whole  solu- 
tion into  a  2-liter  bottle,  through  an  asbestos  filter. 

The  asbestos  is  prepared  by  rubbing  the  ignited  fiber  through 
a  20- mesh  sieve  by  a  gentle  stream  of  water,  receiving  the  water 
and  pulp  in  a  large  vessel,  allowing  the  pulp  to  settle  and  draw- 
ing the  water  off  by  a  siphon.  Cover  the  pulp  with  strong,  hot 
hydrochloric  acid  and  digest  over  night ;  draw  off  the  acid  with 
a  siphon  and  wash  with  water  by  decantation  until  free  from 
acid,  pour  into  a  bottle  with  water  sufficient  to  cover  it,  and 
when  needed  shake  the  bottle  before  drawing  out  a  portion. 

The  purifying  of  the  air  and  oxygen  is  effected  in  an  apparatus 
having  one  side  fitted  to  the  aspirator  bottles  supplying  the  air, 
while  the  other  side  connects  directly  with  the  oxygen  cylinder. 
The  wash-bottles  are  glass-stoppered,  filled  to  \  height  with 
potassium  hydroxide  (sp.  gr.  1.30),  the  attached  calcium-chlo- 
ride jars  filled  to  -J-  height  with  solid  potassium  hydroxide,  and 
the  balance  with  calcium  chloride  and  a  plug  of  glass  wool  on 
top  ;  a  Y-tube  connects  each  side  with  the  combustion-tube. 

The  combustion-tube  is  of  platinum,  J-inch  bore,  with  a  body 
20  inches  long,  having  T3g~inch  platinum  tubes  3  inches  long 
extending  from  the  body.  The  tube  contains  a  roll  of  platinum 
gauze  4  inches  long,  filling  the  bore  of  the  tube  and  pushed  into 
the  combustion-tube  until  the  anterior  end  is  over  the  first  burner; 
this  gauze  is  followed  by  a  roll  i^  inches  long,  of  silver  foil 
inclosed  in  a  piece  of  platinum  foil,  which  just  fills  the  bore  of 
the  tube,  and  this  is  then  followed  by  the  boat,  the  tube  being 
closed  by  a  cone-shaped  ground-joint  which  is  reinforced  by 
bands  of  nickel. 

The  combustion  furnace  is  an  ordinary  lo-burner  Bunsen 
furnace. 

The  absorbing  train  is  made  up  of  two  [j-tubes  giving  a  total 
length  in  tubes  of  44  inches  ;  these  are  followed  by  a  Geissler 
potash  bulb  containing  potassium  hydroxide  solution  (sp.  gr. 
1.30),  (after  a  bulb  has  absorbed  about  \  gram  carbon  dioxide  a 
fresh  one  is  used),  and  a  4-inch  calcium-chloride  tube  contain- 
ing solid  potash.  The  bulb  and  tube  are  weighed,  and  these 
are  followed  by  an  8-inch  calcium-chloride  tube  filled  with  solid 


io  John  S.    Unger. 

potash  to  prevent  any  carbon  dioxide  from  the  outside  air  enter- 
ing the  apparatus.  The  first  l)-tube  of  the  train  is  filled  for  the 
first  5  inches  of  its  length  with  granulated  silver.  This  silver 
is  removed  from  time  to  time  as  it  becomes  dark-colored  on  the 
surface,  ignited,  and  replaced  in  a  tube.  The  silver  is  followed 
by  17  inches  of  calcium  chloride.  In  the  next  l)-tube  there  are  n 
inches  of  calcium  chloride,  then  n  inches  of  anhydrous  copper 
sulphate,  followed  by  a  plug  of  glass  wool.  The  copper  sul- 
phate is  renewed  after  every  five  combustions.  When  the  l)-tubes 
are  first  filled  a  combustion  is  made  in  the  ordinary  manner,  but 
no  weighings  made,  the  object  being  to  saturate  any  caustic 
lime  which  might  be  in  the  calcium  chloride  used.  The  entire 
train  is  supported  on  a  special  support  which  permits  of  adjust- 
ment in  a  vertical  or  horizontal  direction. 

DETERMINATION  OF   MANGANESE   IN   STEEL. 

Weigh  200  milligrams  of  steel  into  a  2-oz.  flask  and  add  20  cc.  of 
1.20  nitric  acid.  When  dissolved,  boil  gently  for  five  minutes, 
remove  and  pour  the  solution  into  a  ico-cc.  graduated  cylinder. 
Wash  out  the  flask  three  times  with  water.  Finally  dilute  to  the 
loo-cc.  mark.  Pour  the  contents  into  a  4-oz.  precipitating  jar  and 
mix  by  pouring  into  a  cylinder  or  jar  at  least  three  times,  draw  off 
25  cc.  with  a  pipette  into  the  flask  in  which  the  solution  was 
made,  add  6  cc.  nitric  acid  (sp.  gr.  1.20)  from  a  burette,  place 
on  a  hot  plate  together  with  a  standard  in  which  the  manganese 
is  exactly  known  and  which  has  been  treated  exactly  like  the 
steel,  and  when  almost  boiling  add  -J  gram  lead  peroxide, 
measured  approximately  on  a  small  glass  spatula,  and  boil  for 
three  minutes.  Remove,  place  in  a  cooling  bath,  and  allow  the 
lead  dioxide  to  settle,  which  usually  requires  fifteen  minutes. 
Decant  the  solution  into  a  comparison  tube  and  compare  with 
the  standard  properly  diluted  as  for  color  carbon  determination. 

DETERMINATION   OF   MANGANESE    IN    PIG    IRON. 

Dissolve  as  for  steel,  place  a  small  funnel  in  the  cylinder,  and 
filter.  Wash  the  residue  thoroughly,  being  careful  not  to  allow 
the  washings  to  exceed  100  cc.,  and  treat  the  filtrate  as  in  the 
case  of  steel. 


Carnegie  Steel  Company,  Homestead,  Pa.  n 

DETERMINATION   OF   NICKED   IN   STEEL. 

Dissolve  i  gram  of  steel  in  25  cc.  nitric  acid  (sp.  gr.  1.20)  and 
boil  in  a  loo-cc.  flask,  until  solution  is  complete.  Wash  con- 
tents of  flask  into  a  ^-gallon  flask  containing  700  cc.  hot  water, 
add  100  cc.  sodium  acetate  solution,  and  bring  to  a  boil  for  one 
minute.  Remove  from  plate  and  let  settle  for  three  minutes, 
filter  through  a  38^-cm.  fluted  filter  into  a  liter  beaker,  and  allow 
the  precipitate  to  run  dry.  To  the  filtrate,  which  should  be  per- 
fectly clear  and  almost  colorless,  add  3  drops  of  phenol-phthalein, 
then  ammonia  until  pink,  place  on  a  hot  plate  and  pass  a  current 
of  hydrogen  sulphide  gas  through  the  solution  for  ten  minutes  ; 
remove  from  the  plate  and  add  12  cc.  acetic  acid  (50  per  cent.), 
stir  and  allow  the  precipitate  to  coagulate  on  a  warm  plate  for  ten 
minutes,  filter  through  a  i2^-cm.  filter  and  wash  with  hydrogen 
sulphide  water  made  slightly  acid  with  acetic  acid.  Roast  in  a 
platinum  crucible,  carefully  at  a  low  red  heat  (usually  at  the 
front  of  a  muffle)  until  the  paper  has  just  burned  off.  Take  out 
crucible  and  break  up  the  precipitate  with  a  platinum  rod  to  pow- 
der, then  place  in  the  muffle  and  ignite  for  fifteen  minutes  at  a 
bright  red  heat,  cool,  and  weigh.  To  the  crucible  add  3  cc. 
hydrochloric  acid  (sp.  gr.  1.20),  cover  with  a  watch-glass  and 
warm  gently  on  a  plate  until  the  precipitate  has  dissolved. 
Wash  into  a  i5o-cc.  beaker  with  water,  add  ammonia  until  the 
solution  smells  strongly  of  ammonia,  and  filter  from  the  silica  and 
ferric  hydroxide.  Redissolve  precipitate  in  3  cc.  hydrochloric  acid 
and  repeat  the  precipitation  with  ammonia,  wash  with  hot  water, 
ignite  in  same  crucible,  and  weigh.  The  difference  in  the  weight 
gives  the  NiO.  A  correction  of  5  per  cent,  on  the  quantity  of 
nickel  present  is  made  to  provide  for  the  nickel  remaining  in  the 
basic  acetate  precipitate. 

The  sodium  acetate  solution  is  made  by  dissolving  3,000  grams 
of  sodium  acetate  in  12  liters  of  water. 


II.  METHODS  USED  AT  THE  LABORATORY  OF  THE 
MONONGAHELA  FURNACE,  McKEESPORT,  PA. 

BY  FREDERICK  CRABTREE. 


DETERMINATION   OP   SILICA   IN   ORES. 

0.5  or  i  gram  of  the  ore  (powdered  to  pass  through  a  100- 
mesh  sieve)  is  fused  with  sodium  carbonate,  the  fusion 
dissolved  in  dilute  hydrochloric  acid,  and  the  solution  evapo- 
rated to  dryness  in  a  5^-inch  or  6-inch  R.  M.  evaporating  dish. 
When  the  residue  is  thoroughly  dry,  dilute  hydrochloric  acid  is 
added  and  the  mixture  boiled  until  the  iron  is  dissolved.  The 
solution  is  then  filtered,  the  silica  washed  with  hot  water, 
ignited,  and  weighed. 

DETERMINATION   OF   IRON    IN   ORES. 

0.5  gram  of  the  ore  is  placed  in  a  2-oz.  beaker  with 
about  35-40  cc.  of  strong  hydrochloric  acid,  and  allowed  to 
stand  on  a  steam-bath  for  several  hours  (usually  over  night) . 
Sometimes  several  drops  of  stannous  chloride  are  added  to 
hasten  the  solution.  When  ready  for  titrating,  the  contents  of 
the  beaker  are  heated  to  boiling  and  examined  to  see  if  the 
residue  is  white  ;  a  slight  excess  of  stannous  chloride  solution 
is  added,  the  mixture  placed  in  a  2O-oz.  beaker  and  diluted 
with  about  300  cc.  of  cold  water.  About  25  cc.  of  cold  satu- 
rated solution  of  mercuric  chloride  are  then  added  and  the  solu- 
tion titrated  with  a  bichromate  solution  containing  about  4.38 
grams  per  liter. 

DETERMINATION   OF   PHOSPHORUS   IN   ORES. 

2  to  5  grams  of  the  ore  are  digested  with  75-150  cc.  of 
strong  hydrochloric  acid  and  the  solution  evaporated  to  hard 
dryness.  About  100  cc.  of  strong  hydrochloric  acid  are  poured 
on  the  residue  and  the  mixture  boiled  until  the  solution  is  con- 
centrated to  about  half  that  volume.  Water  is  then  added  and 


Monongahela  Furnace.  13 

the  diluted  solution  filtered,  keeping  the  volume  of  the  filtrate 
as  small  as  is  convenient. 

The  solution  is  then  evaporated  with  nitric  acid  until  the 
hydrochloric  acid  is  driven  off.  The  insoluble  residue  is 
ignited  and  the  silica  driven  off  by  boiling  with  hydrofluoric  acid. 
The  residue  is  fused  with  sodium  carbonate,  the  fusion  dissolved 
in  nitric  acid,  and  the  solution  filtered  into  the  main  solution. 
To  this  ammonia  water  is  next  added  (the  fluid  is  now  in  a  16- 
oz.  Brlenmeyer  flask)  until  the  solution  becomes  pasty  and 
smells  ammoniacal ;  the  precipitate  is  dissolved  in  a  slight  excess 
of  nitric  acid  and  the  solution  brought  to  a  temperature  of  80° 
C.,  when  40  cc.  of  the  molybdate  solution  are  added. 

A  current  of  air  is  used  to  agitate  the  solution  for  about  five 
minutes  ;  the  latter  is  filtered  while  still  warm.  After  washing 
thoroughly  with  distilled  water,  the  yellow  precipitate  is  titrated 
according  to  the  acidimetric  method.1 

Sometimes  the  method  is  varied  by  not  evaporating  with 
nitric  acid  to  drive  off  hydrochloric  acid  after  filtering  from  the 
insoluble  residue  ;  the  insoluble  residue  may  then  be  fused,  the 
fusion  dissolved  in  nitric  acid,  and  the  solution  evaporated  to 
dry  ness  to  get  rid  of  silica. 

DETERMINATION   OP   MANGANESE   IN   ORES. 

The  filtrate  from  the  silica  determination  is  nearly  neutralized 
by  ammonia,  and  then  ammonium  carbonate  solution  added 
until  the  iron  is  on  the  point  of  coming  down,  the  solution 
still  remaining  clear.  The  addition  of  a  solution  containing 
about  2  grams  of  ammonium  acetate  and  hot  water  enough  to 
give  a  volume  of  about  400-500  cc.,  will  cause  the  precipitation 
of  the  iron  and  aluminum.  The  contents  of  the  beaker  are 
heated  to  boiling  and  boiled  for  about  one  minute.  The  pre- 
cipitate is  filtered  off  and  washed  with  hot  water  immediately. 
The  manganese  in  the  filtrate  is  precipitated  by  bromine  and 
ammonia,  and  usually  weighed  as  Mn3O4. 

DETERMINATION   OF   SIUCON    IN   PIG   IRON. 

i  gram  of  drillings  is  dissolved  in  20  to  25  cc.  of  nitric  acid 

1  Hundeshagen  :  Ztschr.  anal,  Chem.,  1889,  p.  171;  and  Handy:  Proc.  Engineers' So- 
ciety IV.  Pa.,  1892,  p.  78. 


\ 


14  Frederick  Crabtree. 

(1.20)  and  8  to  10  cc.  of  dilute  sulphuric  acid  (1:3)  and  evapo- 
rated in  a  5-inch  R.  M.  dish  until  the  sulphuric  fumes  are  given 
off  copiously.  The  residue  is  treated  with  dilute  hydrochloric 
acid  and  the  mixture  boiled ;  the  residue  is  filtered  off  and  washed 
with  hot  water  and  dilute  hydrochloric  acid,  ignited,  and 
weighed  as  SiO2. 

DETERMINATION   OF   SULPHUR    IN    PIG    IRON. 

The  evolution  method  is  ordinarily  used,  absorbing  the  sul- 
phur in  a  dilute  ammoniacal  solution  of  cadmium  chloride,  and 
titrating  with  iodine  solution  without  filtration. 

DETERMINATION   OF    PHOSPHORUS   IN    PIG    IRON. 

5  grams  of  Bessemer  pig  iron  are  dissolved  in  100  cc. 
of  dilute  nitric  acid  (30  per  cent,  of  nitric  acid  of  1.42  sp. 
gr.);  the  loss  due  to  evaporation  is  made  good  by  diluting 
to  just  loo  cc.,  and  the  solution  then  filtered.  Kighty  cc.  of  the 
filtrate  are  boiled,  oxidized  by  permanganate  solution  and  the 
manganese  oxide  dissolved  by  the  addition  of  hydrochloric  acid. 
The  solution  is  made  ammoniacal  and  the  precipitatere  dissolved 
by  nitric  acid;  to  the  solution,  at  a  temperature  of  75°-8o°  C.,  40 
cc.  of  molybdate  solution  are  added,  and  a  current  of  air  used 
to  agitate  the  liquid  for  about  five  minutes.  The  solution  is 
filtered  while  warm,  the  precipitate  being  washed  with  cold 
water,  and  then  titrated  with  a  caustic  potash  solution,  i  cc.  of 
which  is  equivalent  to  0.0002  gram  phosphorus. 

DETERMINATION   OF   MANGANESE    IN    PIG   IRON. 

Titration  by  Permanganate. — One  gram  of  the  pig  iron  is  dis- 
solved in  dilute  nitric  acid  (25  cc.  water,  15  cc.  nitric  acid  of 
1.42  sp.  gr.)  ;  the  solution  is  evaporated  nearly  to  dryness, 
diluted  with  water,  a  slight  excess  of  zinc  oxide  being  mixed 
with  the  water  added,  and  the  volume  made  up  to  500  cc.  by 
addition  of  water.  After  thoroughly  mixing,  the  precipitate  is 
allowed  to  settle  ;  250  cc.  of  the  supernatant  liquid  are  decanted 
and  titrated  while  hot. 

DETERMINATION   OF   CARBON   IN   STEEL. 

Chromic  Acid  Combustion  Method. — Use  the  following  train  after 


Monongahela  Fwnace.  15 

the  condenser  :  First,  a  small  empty  bottle  ;  second,  pyrogallic 
solution  recommended  by  Committee  on  International  Standards  ; 
third,  silver  sulphate  solution  ;  fourth,  strong  sulphuric  acid  ; 
fifth,  potash  bulb ;  sixth,  small  weighed  flask  containing  sul- 
phuric acid  to  retain  any  moisture  that  might  be  carried  over 
from  potash  bulb ;  seventh,  a  guard  test-tube  containing  sul- 
phuric acid. 

For  dissolving  the  steel  use  a  solution  of  copper  potassium 
chloride  acidified  with  hydrochloric  acid,  and  shake  or  agitate 
so  as  to  have  steel  dissolved  quickly. 

DETERMINATION   OF   SULPHUR   IN   STEEL. 

Iodine  titration  ;  the  process  described  for  pig  iron. 

DETERMINATION   OF   PHOSPHORUS   IN   STEEL. 

4  grams  are  dissolved  in  100  cc.  of  dilute  nitric  acid  (sp.gr. 
1.13),  oxidized  by  permanganate,  the  precipitated  manganese 
oxide  dissolved  by  hydrochloric  acid,  etc.,  as  in  case  of  pig  iron. 

DETERMINATION   OF    MANGANESE   IN   STEEL. 

Color  Method. — 0.2  gram  of  steel  (our  steel  is  soft  and  con- 
tains from  0.25  to  0.45  per  cent,  manganese,  usually)  is  dis- 
solved in  15  cc.  of  dilute  nitric  acid  (sp.  gr.  1.25).  When  the 
solution  is  clear,  and  nitrous  fumes  are  all  expelled,  15  cc.  of  water 
are  added  ;  the  solution  is  brought  to  lively  boiling,  lead  per- 
oxide added,  and  the  mixture  boiled  two  minutes  ;  a  little  more 
lead  peroxide  is  then  added,  when  the  flasks  are  removed  from 
the  hot  plate  and  placed  in  cold  water  for  settling. 


III.  METHODS  USED  AT  THE  LABORATORY  OF  THE 

JUNCTION  IRON  AND  STEEL  COMPANY, 

STEUBENVILLE,  OHIO. 

BY  JOSEPH  M.  WILSON  . 


DETERMINATION   OF  SILICA   IN    IRON   ORES, 

Weigh  i  gram  of  ore  into  a  5-inch  flat  dish,  moisten  with 
10  cc.  water,  add  30  cc.  concentrated  hydrochloric  acid,  evapo- 
rate on  a  hot  plate  to  dryness,  and  ignite.  Moisten  with  hydro- 
chloric acid,  dry,  and  ignite  again.  Cool,  moisten  with  hydro- 
chloric acid,  dissolve  in  30  to  50  cc.  boiling  water,  filter,  wash 
with  hot  hydrochloric  acid  (i  :  i)  and  with  cold  water.  Burn 
the  filter  wet.  Mix  with  5  to  6  parts  sodium  carbonate  and  fuse. 
Dissolve  fusion  in  50  to  60  cc.  water,  add  hydrochloric  acid  till 
acid,  evaporate  to  dryness,  ignite  till  no  further  decrepitation 
occurs,  cool,  moisten  with  hydrochloric  acid,  dry  and  ignite  (to 
render  silica  insoluble),  cool,  and  moisten  with  hydrochloric  acid  ; 
take  up  in  boiling  water,  filter,  and  wash  twice  alternately  with 
hot  hydrochloric  acid  ( i  :  i )  and  cold  water  ;  then  five  or  six 
times  with  hot  water.  Burn  and  weigh  as  SiOa. 

If  greater  accuracy  be  desired,  moisten  the  silica  with  hydro- 
fluoric acid  and  add  a  few  drops  of  sulphuric  acid.  Evaporate 
to  dryness,  ignite,  cool,  and  weigh.  The  loss  =  SiO2. 

DETERMINATION   OF   IRON    IN   ORES. 

The  following  solutions  are  employed  :  Potassium  dichromate, 
4.9  grams  dissolved  in  one  liter  of  water;  i  cc.  =  0.005  gram 
Fe.  Stannous  chloride,  100  grams  dissolved  in  i  liter  of  hydro- 
chloric acid  (i  :  i).  Mercuric  chloride,  50  grams  dissolved  in  i 
liter  of  water.  Potassium  ferricyanide,  a  piece  one-fourth  the 
size  of  a  pea  in  40  cc.  water. 

Weigh  0.25  and  0.5  gram  ore  into  small  unlipped  beakers, 
moisten  with  water,  add  30  cc.  hydrochloric  acid,  cover,  and  place 
on  a  steam  table  ;  when  solution  is  complete  and  residue  appears 


Junction  Iron  and  Steel  Company.  17 

white,  boil  on  a  hot  plate,  add  stannous  chloride  from  a  pipette  till 
the  liquid  becomes  colorless,  boil  a  few  moments,  remove  to  steam 
table  till  ready  to  titrate,  wash  into  beaker,  dilute  to  300-350  cc., 
stir,  pour  in  excess  of  mercuric  chloride  (30  to  40  cc.),  stir,  run 
in  potassium  dichromate  at  once  until  four  drops  fail  to  develop 
a  blue  color  with  ferricyanide  indicator  in  one-half  minute. 
Burette-reading  on  half-gram  samples  gives  the  per  cent,  of  iron 
when  i  cc.  potassium  dichromate  =  0.005  gram  iron.  Reading 
on  \  gram  doubled  should  vary  not  more  than  0.2  cc.  from  that 
on  \  gram. 

Precautions. — Avoid  large  excess  of  stannous  chloride  ;  one  or 
two  drops  more  than  is  required  to  destroy  yellow  color  is  suffi- 
cient. 

In  adding  mercuric  chloride  pour  all  in  at  once.  If  added 
slowly,  metallic  mercury  is  precipitated  and  the  operation 
spoiled. 

DETERMINATION   OF   PHOSPHORUS   IN   ORES. 

Weigh  10  grams  ore  into  a  5 -inch  (deep)  dish,  moisten  with 
water,  and  add  100  cc.  hydrochloric  acid ;  let  stand  on  steam 
table,  evaporate  to  dryness,  heat,  cool,  moisten  with  100  cc. 
hydrochloric  acid  ;  boil  down  to  a  syrup,  add  75  cc.  water,  filter, 
and  wash  with  hydrochloric  acid  ( i  :  i )  and  cold  water.  Ignite 
residue,  fuse  with  5  to  6  parts  of  sodium  carbonate,  dissolve  the 
fusion  in  water  and  hydrochloric  acid,  evaporate  to  dryness  and 
heat,  moisten  with  hydrochloric  acid,  take  up  with  water,  filter, 
boil  filtrate,  and  add  a  slight  excess  of  ammonia.  Filter,  wash 
two  or  three  times  with  hot  water,  dissolve  in  hot  nitric  acid  of 
1.2  specific  gravity,  add  to  main  solution,  which  has  in  the 
meantime  been  evaporating  to  a  syrup;  add  75  cc.  nitric 
acid  and  again  evaporate  to  a  syrup  ;  transfer  to  a  i6-oz.  flask 
and  add  an  excess  of  ammonia ;  redissolve  the  precipitate  in 
nitric  acid  in  very  slight  excess,  warm  to  87°  C.,  add  50-75  cc.  of 
molybdate  solution,  shake  five  minutes,  and  allow  to  settle;  filter 
and  wash  with  ammonium  sulphate  solution  till  free  from  iron. 

The  ammonium  sulphate  solution  is  made  by  diluting  and 
mixing  48  cc.  sulphuric  acid  and  55  cc.  ammonia,  and  then 
making  up  to  2  liters. 


1 8  Joseph  M.    Wilson. 

The  molybdate  solution  is  prepared  according  to  Woods' 
formula.1 

A  stream  of  air  is  blown  through  the  liquid  while  adding  the 
molybdate  solution. 

The  yellow  precipitate  is  dissolved  in  ammonia,  5  to  10  cc- 
magnesia  mixture  are  added,  the  liquid  well  stirred  and  allowed 
to  stand  for  two  hours  ;  filter  and  without  washing  redissolve 
the  precipitate  in  hydrochloric  acid.  The  bulk  of  the  liquid 
must  be  kept  below  25  cc.  A  piece  of  citric  acid  half  the  size 
of  a  pea  is  added  and  then  ammonia  in  slight  excess.  After 
stirring,  the  liquid  is  set  aside  for  fifteen  to  twenty  minutes,  stir- 
ring occasionally.  The  solution  is  now  diluted  with  an  equal 
bulk  of  ammonia  and  allowed  to  stand  from  twelve  to  twenty- 
four  hours.  Filter,  using  a  Gooch  crucible  ;  wash  with  a  solu- 
tion of  ammonium  nitrate  containing  50  grams  ammonium 
nitrate  in  2  liters  nitric  acid  (i  :  3)  ;  burn  and  weigh.  Or,  the 
yellow  precipitate  is  dissolved  in  sodium  hydroxide  and  titrated 
with  standard  nitric  acid,  according  to  Hundeshagen,2  or,  the 
precipitate  is  dissolved  in  ammonia,  the  solution  acidulated  with 
sulphuric  acid  and  the  phosphorus  determined  volumetrically  by 
permanganate,  according  to  Emmerton.3 

DETERMINATION    OF     MANGANESE     IN     ORES   AND    IN    METALS. 

Volhard's  Method :  This  method  was  described  by  Bmmerton4 
and  is  as  follows  :  * '  Evaporate  solution — peroxidized — with 
sulphuric  acid,  in  excess,  till  copious  fumes  are  evolved  ;  cool, 
take  up  in  water,  filter  into  a  3oo-cc.  graduated  flask,  add 
sodium  carbonate  till  color  is  wine-red,  but  no  precipitate  forms  ; 
then  zinc  oxide  suspended  in  water  till  color  is  light  brown  (or 
perhaps  fawn),  mix  by  pouring  into  beaker  and  back  several 
times,  filter  through  a  ic-inch,  dry,  fluted  filter,  take  200  cc.  of  fil- 
trate in  a  i6-oz.  flask,  to  which  add  2  drops  nitric  acid  (sp.  gr. 
1.42),  boil,  run  in  potassium  permanganate  a  little  at  a  time, 
shake  vigorously  to  make  precipitate  collect,  allow  to  settle,  and 
repeat  till  a  permanent  pink  is  obtained. 

1  Proc.  Engineers*  Society  W.  Pa.,  8,  80,  1892. 

2  Ztschr.  anal.  Chem.,  1889,  171. 

8  Blair's  Analysis  of  Iron,  Second  Udition,  p.  85. 
*  Trans.  A .  I.  M.  £.,  10,  204. 


Junction  Iron  and  Steel  Company.  19 

Notes. — This  method  is  not  applicable  to  substances  contain- 
ing less  than  0.8  percent,  manganese  owing  to  the  difficulty 
in  distinguishing  the  color  of  manganese  dioxide,  from  the  pink 
of  potassium  permanganate.  When  the  substance  contains 
more  than  5  per  cent. ,  take  100  cc. ,  or  even  less,  instead  of  200  cc. 

Pig  iron  is  to  be  treated  as  for  silicon,  then  filtered,  the  filtrate 
evaporated  a  second  time  with  sulphuric  acid,  proceeding  then 
as  above  described. 

The  permanganate  solution  contains  1.27  grams  potassium 
permanganate  per  liter. 

i  cc.=  0.002262  gram  Fe,  or  0.000666  gram  Mn,  correspond- 
ing to  o.  i  per  cent,  manganese  when  f  gram  of  the  sample  is 
used. 

Color  Method. — Weigh  0.2  gram  of  the  sample  into  an  n- 
inch  tube,  add  20  cc.  nitric  acid  (sp.  gr.  1.20),  boil  till  the 
escape  of  brown  fumes  ceases,  add  10  cc.  of  water,  boil,  add  about 
3  grams  lead  dioxide,  and  continue  boiling  for  two  and  one-half 
minutes.  Place  in  cold  water  until  the  liquid  has  become  clear; 
decant  into  the  reading  tube  and  compare. 

Use  pig  iron  or  steel  in  which  the  manganese  has  been  deter- 
mined gravirnetrically  :  (a)  By  Ford's  method  ;  (b)  by  acetate 
method,  as  a  standard.  (Weigh  standard  with  each  batch  to  be 
read.)  Manganese  is  also  determined  by  precipitation  by  bro- 
mine, and  weighing  as  Mn3O4. 

DETERMINATION   OF    SILICON   IN   PIG   IRON. 

Brown's  method  is  used. 

DETERMINATION   OF   SULPHUR    IN    PIG   IRON. 

By  method  described  by  Kmmerton1  absorption  of  hydrogen 
sulphide  in  potassium  hydroxide  (Powers  and  Weightman's  white 
stick  caustic  is  the  only  brand  that  will  give  uniformly  correct 
results)  and  titration  with  iodine  solution,  i  cc.  =  0.0005  gram 
sulphur.  Standardize  by  a  steel  of  known  sulphur  content. 
Results  check  with  those  obtained  by  the  aqua  regia  method. 
When  solution  is  complete,  boil  till  steam  reaches  the  stopper  of 
the  first  tube,  remove  flame,  open  the  stop-cock  in  the  funnel,  and 

1  Trans.  A.  I.  M.E.,  10. 


20  Junction  Iron  and  Steel  Company. 

allow  to  stand  till  liquid  in  tube  is  cold.  Wash  into  a  beaker, 
making  the  volume  up  to  300-400  cc.,  add  3-5  cc.  starch  solution, 
then  excess  of  hydrochloric  acid,  titrate  with  iodine  solution,  of 
which  i  cc.  =  0.0005  gram  sulphur.  Standardize  the  iodine 
solution  with  steel  or  pig  iron,  the  sulphur  content  of  which 
has  been  determined  as  indicated. 

Precautions. — Be  sure  that  the  metal  is  entirely  dissolved. 
Pig  irons  high  in  sulphur  frequently  dissolve  very  slowly  and 
must  be  watched  carefully.  The  method  for  sulphur  determina- 
tion described  by  N.  W.  lyord1  is  to  be  highly  recommended. 

DETERMINATION    OF   PHOSPHORUS   IN    PIG   IRON. 

Follow  Emmerton  till  the  yellow  precipitate  is  obtained,  then 
Hundeshagen,2  and  Handy.3 

DETERMINATION    OF    MANGANESE   IN   PIG   IRON. 

Color  method,  using  a  pig  iron  standard  ;  also  Ford's  method 
for  the  purpose  of  checking. 

DETERMINATION   OF    CARBON   IN   STEEL. 

Ullgren's  method,  as  described  by  McCreath,4  is  followed, 
checking  by  combustion  in  a  platinum  tube.  As  the  solvent, 
ammonio-cupric  chloride,  in  saturated  solution,  is  used. 

The  chromic  acid  solution  contains  80  cc.  concentrated  sul- 
phuric acid  (previously  purified  by  the  addition  of  a  little  chromic 
acid)  and  10  cc.  of  a  saturated  solution  of  chromic  acid  crystals. 
Not  more  than  20  cc.  of  water  are  used  in  rinsing  the  carbon 
into  the  combustion  flask.  Soda-lime  is  the  absorbent  for  the 
carbon  dioxide  evolved. 

The  methods  for  the  determination  of  sulphur  and  phosphorus 
are  the  same  as  in  the  case  of  cast  iron. 

Manganese  is  determined  by  color ;  checking  by  Ford's 
method. 

Nickel  is  determined  according  to  the  method  of  Eastwick. 

1  Notes  on  Metallurgical  Analysis,  p.  5-2. 

2  Loc.  tit. 

8  Proc.  Engineers'  Society  IV.  Pa.,  1892,  p.  78. 
4  Trans.  A.  I.  M.  E.,  5,  575. 


IV.  METHODS  USED  AT  THE  LABORATORY  OF  THE 
CARNEGIE  STEEL  COMPANY,  LUCY  FUR- 
NACE, PITTSBURG,  PENNA. 


BY  ROBERT  MILLER. 


DETERMINATION    OF    SILICA,  IRON,    AND    PHOSPHORUS  IN  IRON 

ORES. 

I  use  the  methods  described  on  pages  16,  19,  22-26,  respect- 
ively, of  "  Notes  on  Metallurgical  Analysis,"  by  N.  W.  Lord. 

DETERMINATION  OF  SILICON  AND  SULPHUR  IN  PIG  IRON. 

On  pages  37  and  35,  respectively,  of  the  above  work,  will  be 
found  described  the  methods  used  by  me  for  this  purpose. 

DETERMINATION  OF  MANGANESE  IN  PIG  IRON. 

Volhard's  method,  as  described  by  Blair1,  is  used  for  this  de- 
termination. 

DETERMINATION  OF  PHOSPHORUS  IN  PIG  IRON. 

Weigh  off  i  to  5  grams  of  iron  (according  to  the  amount  of 
phosphorus  present) ,  put  into  a  4-oz.  beaker,  and  add  cautiously 
25-75  cc.  nitric  acid  (sp.  gr.  1.20).  After  the  violent  action 
has  ceased,  boil  down  to  dryness,  and  bake  for  thirty  minutes. 
Allow  to  cool,  dissolve  the  mass  in  20-40  cc.  of  concentrated 
hydrochloric  acid,  and  evaporate  the  solution  to  10  cc.  Add  20 
cc.  of  water  and  filter.  Now  add  ammonia  until  ferric  hydroxide 
separates  out,  and  the  mass  becomes  thick  and  smells  of  the  pre- 
cipitant. Redissolve  the  precipitate  in  strong  nitric  acid,  adding 
the  acid  gradually  and  until  the  liquid  has  an  amber  color. 
Without  previously  heating  the  solution,  add  40  cc.  of  molybdic 
acid  and  allow  the  yellow  precipitate  to  settle.  The  phosphorus 
is  all  down  in  about  ten  minutes.  Filter  on  a  Q-cm.  filter  and 
wash  with  acid  ammonium  sulphate.  Dissolve  the  precipitate 
in  5  cc.  of  strong  ammonia  (diluted  with  25  cc.  of  water)  and  allow 
to  run  jinto  the  flask  in  which  the  precipitation  was  made. 

1  Blair's  Analysis  of  Iron,  Third  Edition,  p.  118. 


22  Carnegie  Steel  Company,  Pittsburg,  Pa. 

Wash  the  filter  until  the  volume  of  the  filtrate  is  150  cc.  Add 
10  cc.  of  concentrated  sulphuric  acid,  dilute  to  200  cc.  and  filter 
through  the  reductor.  The  reduced  solution  is  titrated  with 
potassium  permanganate. 

The  acid  ammonium  sulphate  used  in  washing  the  yellow 
precipitate  is  made  by  adding  27.5  cc.  of  ammonia  (sp.  gr.  0.96) 
to  500  cc.  of  water,  to  this  24  cc.  of  strong  sulphuric  acid  (C.  P.), 
and  making  the  whole  up  to  i  liter. 

To  prepare  the  molybdic  acid  solution,  add  to  100  grams  of 
molybdic  acid  200  cc.  of  water  and  then  160  cc.  of  ammonia. 
This  dissolves  all  the  acid.  Pour  the  filtered  solution  into  i 
liter  of  nitric  acid  (sp.  gr.  1.20).  Allow  the  mixture  to  stand  a 
day  or  two  before  using. 


V.  METHODS  USED  AT  THE  LABORATORY  OF  THE 

BLACK  DIAMOND  STEEL  WORKS, 

PITTSBURG,  PA. 


BY  EDWARD  S.  JOHNSON. 


I.    IRON  ORBS. 

1.  Silica. — i    to    3  grams  of  the   finely   pulverized   ore   are 
digested  upon  the  water-bath  in  a  covered  beaker  with  10  to  30 
cc.  of  concentrated  hydrochloric  acid  until  decomposition  is  com- 
plete.    The  solution  and  silicious  residue  are  then  transferred 
to  a  porcelain  dish,  and  the  solution  evaporated  on  the  graphite- 
bath  (substitute  for  the  sand-bath)  to  dryness.     The  residue  is 
taken  up  with  concentrated  hydrochloric  acid  and  water,  the 
solution  evaporated  as  before,   and,  after  redissolving  the  dry 
mass  in  concentrated  acid  and  dilution  with  several  volumes  of 
water,  the  silicious  residue  is  collected  upon  a  Swedish  filter, 
thoroughly  washed,  and  ignited  in  a  platinum  crucible.     After 
ignition  the  residue  is  subjected  to  a  fusion  with  ten  to  fifteen 
times  its  weight  of  sodium  carbonate.     The  fusion  is  dissolved 
in  water  and  hydrochloric  acid,  the  solution  evaporated  to  dry- 
ness  on  the  water-bath,  and  the  separation  of  the  silica  further 
conducted  as  usual  under  the  given  circumstances.     The  insolu- 
ble residue  remaining  after  the  fusion,  etc.,  is  weighed  ordinarily 
as  SiOa. 

In  still  more  accurate  determinations,  the  silica  thus  obtained 
is  treated  with  hydrofluoric  and  sulphuric  acids.  The  loss  after 
evaporation  and  ignition  is  silica. 

2.  Iron. — The  process  for  the  determination  of  iron  in  iron 
ores  is  the  familiar  one,  consisting  in  the  solution  of  the  ore  in 
the  least  possible  quantity  of  concentrated  hydrochloric  acid,  re- 
duction of  the  resulting  ferric  or  ferro-ferric  to  a  ferrous  solution, 
and  titration  of  the  highly  dilute  solution,  in  the  presence  of  a 
large  excess  of  sulphuric  acid,  with  potassium  permanganate. 

0.4  to  0.5   gram  of  the  sample    is   dissolved    in  a   covered 


24  Edward  S.  Johnson. 

lo-inch  by  i-inch  test-tube  in  4  to  5  cc.  of  concentrated  hydro- 
chloric acid.  The  tube  is  heated  over  a  small  gas  flame,  at  first 
only  warmed,  and  later,  as  the  reaction  proceeds,  to  gentle  boil- 
ing. A  small  crystal  (o.i  to  0.2  gram)  of  potassium  chlorate  is 
added  to  the  solution  to  oxidize  possibly  present  organic  matter, 
and  the  boiling  continued,  with  addition  of  more  hydrochloric 
acid,  if  necessary,  for  some  minutes  in  order  to  decompose  an 
excess  of  chlorate. 

When  all  but  a  flocculent  silicious  residue  has  been  dissolved 
(the  watch-glass  covering  the  tube) ,  the  walls  of  the  tube  are 
rinsed  down  with  water,  and  3  to  4  grams  of  triturated  zinc 
added  to  the  solution.  The  resulting  brisk  evolution  of  hydro- 
gen soon  slackens  ;  a  few  cubic  centimeters  of  dilute  sulphuric 
acid  (i  :  i)  are  poured  into  the  tube,  and  heat  is  applied,  with 
addition  of  more  dilute  sulphuric  acid  as  required,  until  the 
colorless  condition  of  the  solution  indicates  the  complete  reduc- 
tion of  ferric  salt,  and  all  zinc  has  dissolved.  The  remainder  of 

25  cc.  of  concentrated  sulphuric  acid  (diluted  with  i  volume  of 
water)  is  next  added,  and  the  reduced  solution  transferred  from 
the  test-tube  to  a  6oo-cc.  beaker.     Sufficient  cold,  freshly-boiled 
distilled  water,  to  make  the  volume  of  the  solution 400  to  500 cc., 
is  poured  into  the  beaker.    From  a  5o-cc.  Gay-L,ussac  burette,  a 
solution  of  potassium  permanganate   (i  cc.  representing  about 
0.0068  gram  of  iron) ,  standardized  by  oxalic  acid,  is  run  into 
the  diluted  ferrous  solution  until  finally  one  drop  imparts  to  it  a 
permanent  pink  coloration .  From  the  number  of  cubic  centimeters 
used  in  the  titration,  a  deduction  is  made  for  the  volume  of  per- 
manganate solution  required  to  produce  the  above  end-reaction 
with  all  materials  present  or  applied  in  the  operations  just  de- 
scribed, /.  <?.,   acids,   zinc,   ferric  chloride,  water,  etc.     The  re- 
mainder forms  obviously  the  basis  for  the  calculation  of  the  per- 
centage of  iron. 

3.  Phosphorus. — This  element  is  separated  as  ammonium 
phosphomolybdate  and  weighed  in  the  same  form. 

1.63  grams  of  ore  are  weighed  off  into  a  small  porcelain  dish 
and  ignited  gently.  When  it  has  sufficiently  cooled,  the  sam- 
ple is  treated  with  about  20  cc.  of  concentrated  hydrochloric 
acid,  and  the  mixture,  with  frequent  stirring,  is  heated  on  the 


Black  Diamond  Steel  Works.  25 

water-bath  until  all  but  silicious  matter  has  dissolved.  The 
solution  is  evaporated  to  dry  ness,  and  the  residue  redissolved  in 
20  to  30  cc.  of  hydrochloric  acid.  This  second  hydrochloric  acid 
solution  is  evaporated  until  the  separation  of  basic  chloride  of  iron 
begins.  With  two  or  three  drops  of  acid,  the  solution  is  restored; 
30  to  40  cc.  of  water  are  added,  and  the  insoluble  silicious  residue  is 
filtered  off.  The  filtrate,  which  should  have  a  volume  of  about 
60  cc.,  is  ready  for  the  precipitation  which  is  effected  as  de- 
scribed for  steel,  p.  32. 

4.  Manganese. — According  to  the  percentage  of  manganese 
present,  the  colorimetric  or  a  gravimetric  method  is  applied  for 
its  quantitative  determination  :  for  quantities  up  to  about  three 
per  cent.,  the  former;  for  higher  percentages,  the  latter. 

A.    COLORIMETRIC  METHOD. 

From  0.05  to  o.io  gram  of  ore  is  placed  in  a  6-inch  by  ^--inch 
test-tube,  and  dissolved  in  2  to  3  cc.  of  concentrated  hydrochloric 
acid  which  is  then  expelled  by  boiling  with  an  excess  of  concen- 
trated nitric  acid  of  1.42  sp.  gr.  The  nitric  acid  solution  is 
poured  into  a  lo-inch  by  i-inch  test-tube,  rinsed  out  of  the  smaller 
tube  with  32  per  cent,  nitric  acid,  and  diluted  with  the  same  to 
a  volume  of  about  35  cc.  By  the  addition  of  lead  peroxide 
and  boiling  the  solution,  manganese  is  oxidized  to  permanganic 
acid  and  determined  in  this  form,  as  directed  for  the  estimation, 
of  manganese  in  steel,  p.  33. 

B.    GRAVIMETRIC  METHOD. 

For  quantities  over  3  per  cent.,  the  colorimetric  method  is 
as  yet  scarcely  longer  available1  ;  a  gravimetric  determination  is 
then  resorted  to.  The  usual  practice  is  to  separate  the  manga- 
nese from  a  nitric  acid  solution  in  presence  of  a  large  excess  of 
strong  nitric  acid  by  precipitation  with  potassium  chlorate  as 
hydrated  dioxide.  The  latter  is  separated  by  filtration,  washed 
with  strong  nitric  acid,  and  redissolved  in  sulphurous  acid. 
The  manganese  in  this  solution  is  finally  freed  whol!}1"  from  iron 
by  a  basic  acetate  precipitation.  In  the  filtrate  from  the  iron 
precipitate,  manganese  is  precipitated  in  the  form  of  ammo- 
nium manganese  phosphate. 

1  Experiments,  with  the  object  of  determining  the  maximum  percentage  which  may 
be  estimated  colorimetrically,  are,  however,  in  progress. 


26  Edward  S.  Johnson. 

II.    PIG  IRON. 

i.  Silicon.  —  i  gram  of  metal  is  dissolved  in  a  small,  covered, 
porcelain  dish  in  10  cc.  of  dilute  sulphuric  acid  (1:3)  with  the 
addition  of  an  equal  volume  of  water.  The  action  of  the  acid  is 
hastened  by  heating.  When  the  evolution  of  hydrogen  has 
ceased,  the  cover-glass  is  rinsed  off  into  the  dish,  and  the  latter 
placed  on  the  graphite-bath,  where  the  contents  of  the  dish  are 
heated  until  dense  white  fumes  of  sulphuric  anhydride  form 
abundantly.  The  dish  is  removed  from  the  bath,  allowed  to 
cool  somewhat,  and  the  residue  treated  with  water.  Heat  and 
stirring  are  applied  until  all  sulphate  of  iron  has  dissolved.  The 
insoluble  residue  is  filtered  off,  washed  with  water  and  dilute 
hydrochloric  acid  until  free  from  iron,  ignited,  and  weighed  as 
SiO8.  If  S  represent  the  weight  of  metal  taken  for  the  deter- 
mination, SiO^  the  weight  of  silica  found,  and  Si  the  percentage 
of  silicon,  then 

c-_ 


2.  Sulphur.  —  The  method  adopted  for  the  estimation  varies 
with  the  variety  of  iron  and  the  accuracy  required.  For  gray 
iron  and  "commercial"  accuracy,  the  evolution-volumetric 
method  is  applied  ;  for  white  iron  and  also  gray  varieties  of  pig 
iron,  when  the  utmost  accuracy  is  demanded,  the  aqua  regia 
method  is  made  use  of. 

A.    EVOUJTION-VOUJMETRIC  METHOD. 

The  details  of  the  process  are  given  below  in  the  description 
of  methods  for  the  analysis  of  steel,  p.  30. 

B.    AQUA  RKGIA  METHOD. 

The  sample  —  about  5  grams  —  is  dissolved  in  concentrated 
nitric  acid  of  1.42  sp.  gr.,  with  the  addition  of  a  small  quantity  of 
hydrochloric  acid  —  a  few  cubic  centimeters  of  concentrated  acid 
at  a  time  —  and  by  the  aid  of  heat,  when  necessary,  to  start  the 
dissolving  of  the  borings.  When  the  action  of  the  acid  has 
ended,  about  2  grams  of  sodium  carbonate  are  added,  and  the 
solution  is  warmed  until  the  escape  of  carbon  dioxide  has 


Black  Diamond  Steel   Works.  27 

ceased.  Silica  is  separated  as  usual  by  evaporation  to  dry  ness, 
solution  of  the  residue  in  hydrochloric  acid,  and  filtration.  The 
slightly  acid  filtrate  is  diluted  to  75  to  100  cc.  for  each  gram  of 
metal  taken  for  the  determination,  and  treated,  while  at  a  boil- 
ing temperature,  with  a  hot  solution  of  barium  chloride  in  mod- 
erate excess.  After  the  mixture  has  stood  several  hours,  the 
precipitate  of  barium  sulphate  is  collected  on  a  washed  Swedish 
filter,  and  washed  as  usual  with  hot  water  and  dilute  hydro- 
chloric acid  (i  :  20).  Should  the  precipitate  be  contaminated 
with  oxide  of  iron,  a  separation  of  the  latter  by  fusion  with 
sodium  carbonate,  etc.,  is  undertaken  after  ignition. 

3.  Phosphorus. — The  details  of  the  method  for  the  determina- 
tion of  phosphorus  in  pig  iron  are  essentially  the  same  as  in  the 
case  of  steel.     1.63  grams  of  borings  are  dissolved  in  50  cc.  of  20 
per  cent,  nitric  acid.     The  insoluble  carbonaceous  and  siliceous 
matter  is  filtered  off,  and  the  filtrate — about  60  cc.   in  volume — 
is  treated  as  directed  on  p.  32. 

4.  Manganese. — The  same  considerations  and  practice  apply 
in  the  determination  of  manganese  in  pig  iron  as  in  the  estima- 
tion of  that  element  in  steel,  see  p.  33. 

in.  STEBi,. 

i.  Carbon. — In  order  to  determine  the  carbon  in  steel,  the 
separation  is  accomplished  by  decomposing  the  metal,  as  gen- 
erally customary,  by  means  of  cupric  potassium  chloride.  As 
is  well  known,  a  residue  containing  the  whole  of  the  carbon  re- 
mains after  the  action  of  the  double  chloride.  By  combustion 
in  a  stream  of  oxygen,  the  carbon  of  the  residue  is  converted  for 
weighing  into  carbon  dioxide. 

According  to  the  amount  of  carbon  present,  i  to  10  grams  of 
steel  are  treated  with  the  above-mentioned  solution  (3Oto4occ. 
for  each  gram  of  metal)  of  cupric  potassium  chloride  which  is 
made  by  dissolving  1 2  grams  of  a  pure  preparation  of  the  salt  in  3 
liters  of  water  and  50  cc.  of  concentrated  hydrochloric  acid,  and 
filtration  of  the  solution  through  ignited  asbestos. 

The  mixture  of  chloride  and  steel  borings  is  constantly 
stirred,  warmed  at  first,  and  finally  heated  to  about  100°  C.  un- 
til the  metallic  copper  which  separates  in  the  reaction  is  redis- 


28  Edward  S.  Johnson. 

solved.  Sufficient  dilute  hydrochloric  acid  (i  :  i)  is  added  to 
dissolve  the  basic  chlorides  of  iron  and  copper,  which  may  sepa- 
rate out  toward  the  end  of  the  above  operation,  and  keep  them 
in  solution  during  the  subsequent  filtration.  This  is  effected  by 
Dr.  Blair's  familiar  device  for  the  purpose,  consisting,  as  need 
scarcely  be  added,  of  a  platinum  boat,  with  a  finely  perforated 
bottom,  and  a  funnel  of  the  same  metal,  into  which  the  boat 
may  be  tightly  packed  with  asbestos  to  allow  of  the  use  of  the 
filter-pump.  The  packing  is  done  by  means  of  asbestos  in  the 
form  of  pulp  such  as  is  also  used  in  forming  a  felt  filter  over  the 
perforations  in  the  boat.  The  pulp  for  the  felt  may  be  conve- 
niently made  by  heating  asbestos  wool  to  redness,  cutting  the 
fibers  into  short  pieces  with  the  scissors  (a  manipulation  ren- 
dered much  easier  by  the  preparatory  heating),  and,  after  a 
second  ignition,  agitating  witn  water. 

When  the  carbonaceous  residue  has  been  collected  in  the 
boat,  washed  thoroughly  with  dilute  hydrochloric  acid  and 
water,  and  dried  at  100°  C.,  it  is  ready  for  combustion. 

The  latter  is  carried  out  in  a  porcelain  tube  of  the  usual  di- 
mensions, heated  in  a  ten-burner,  Bunsen  combustion  furnace, 
and  supplied  with  a  slow  stream  of  oxygen  purified  by  passage 
over  red-hot  copper  oxide  and  through  absorbents  for  water  and 
carbon  dioxide,  in  the  following  order  :  Through  potassium 
hydroxide  solution  (i  :  2),  and  over  granulated  calcium  chloride 
and  soda-lime. 

The  combustion-tube,  projecting  four  or  five  inches  beyond 
the  furnace  at  either  end,  is  filled,  excepting  the  projecting  ends 
and  enough  space  in  the  rear  for  the  reception  of  the  boat,  with 
coarsely  granular,  copper  oxide  which  is  kept  in  place  by  short, 
spiral  rolls  of  copper  gauze.  Rubber  stoppers  at  the  rear  and 
front  ends  of  the  tube  connect,  respectively,  with  the  supply  of 
oxygen  and  the  apparatus  for  the  purification  and  absorption  of 
the  carbon  dioxide  formed  in  the  combustion-tube.  The  possi- 
ble impurities  which  require  removal  are  hydrochloric  acid  and 
chlorine.  The  gases  issuing  from  the  front  end  of  the  tube  are, 
therefore,  caused  to  pass  first  through  a  saturated  solution  of 
ferrous  sulphate  acidulated  with  a  few  drops  of  dilute  sulphuric 
acid,  where  any  chlorine  in  the  mixture  is  converted  into  hydro- 


Black  Diamond  Steel  Works.  29 

chloric  acid,  and  any  of  the  latter  substance  in  the  gases  is 
mainly  absorbed.  Should  hydrochloric  acid  escape  absorption 
in  the  ferrous  sulphate  solution,  it  is  retained  by  the  saturated 
solution  of  silver  sulphate  which  follows.  The  gases  leaving 
the  silver  solution  are  saturated  with  vapor  of  water.  By  pass- 
ing them  through  concentrated  sulphuric  acid  and  over  calcium 
chloride  they  are  completely  dried,  and  may  enter  the  Geissler 
potash  bulbs  which  immediately  follow,  and  in  which  the  ab- 
sorption of  their  carbon  dioxide  takes  place.  The  bulbs  are 
filled  with  potassium  hydroxide  solution  (1:2);  to  prevent  loss 
of  moisture  from  the  solution  by  the  continuous  passage  of  gas 
through  the  apparatus,  the  bulbs  are  fitted  with  a  cover- tube, 
with  ground-joint,  containing  solid  potassium  hydroxide. 

Connected  with  the  exit-end  of  the  potash  bulbs,  a  6-inch, 
straight,  calcium-chloride  tube,  filled  also  with  pieces  of  potas- 
sium hydroxide,  protects  them  against  the  possibility  of  the  en- 
trance of  moisture  and  carbon  dioxide  from  the  atmosphere.  It 
concludes  the  train  of  apparatus  attached  to  the  front  end  of  the 
combustion-tube. 

After  the  familiar  preliminaries  of  introducing  the  boat  with 
its  carbonaceous  residue,  weighing  and  attaching  the  potash 
bulbs,  securing  all  connections,  and  starting  a  slow  stream  of 
oxygen  through  the  apparatus,  the  combustion  is  begun  by 
heating  the  front  half  of  the  porcelain  tube  to  redness.  The  rest 
of  the  tube  containing  the  boat  is  then  gradually  heated  to  the 
same  temperature.  For  fifteen  to  twenty-five  minutes  a  red  heat 
is  maintained  and  the  passage  of  oxygen  continued.  The  oxy- 
gen is  then  cut  off,  and  air  from  an  independent  drying  and 
purifying  apparatus — a  duplicate  of  that  described  for  use  with 
oxygen — is  drawn  during  forty-five  to  sixty  minutes  slowly 
through  the  entire  apparatus.  By  this  manipulation  all  carbon 
oxide  is  brought  into  the  potash  bulbs,  and  the  latter  filled  with 
air.  To  insure  a  complete  displacement  of  the  oxygen  in  the 
potash  bulbs,  after  the  main  aspiration,  air  which  has  been  freed 
from  carbon  dioxide  is  drawn  for  some  minutes  through  the  dry- 
ing apparatus  directly  behind  the  bulbs,  and  the  bulbs  them- 
selves. 

The  potash  apparatus  is  detached  and  allowed  to  stand  fifteen 


30  Edward  S.  Johnson. 

to  twenty  minutes  in  the  balance  case,  where  it  had  stood  for  at 
least  the  same  length  of  time  before  the  first  weighing.  The 
increase  in  weight  is  ascertained,  and  therefrom  the  percentage 
of  carbon  deduced  according  to  the  well-known  formula. 

2.  Sulphur. — The  determination  is  effected  by  separating  the 
element  as  cadmium  sulphide  and  estimating  the  sulphur  in  the 
latter  volumetrically  with  iodine  solution. 

The  metal  is  dissolved  in  dilute  hydrochloric  acid  ;  the  gases 
evolved  are  passed  into  a  strongly  ammoniacal  solution  of  cad- 
mium chloride  in  which  the  sulphur,  entering  as  hydrogen 
sulphide,  is  precipitated.  The  precipitate  is  filtered  off,  dis- 
solved in  a  large  volume  of  dilute  hydrochloric  acid,  and  the 
hydrogen  sulphide  again  set  free,  measured  as  indicated  above. 

The  solution  of  the  sample  is  carried  out  in  a  25O-cc.  Florence 
flask. 

Into  the  neck  of  the  flask  is  fitted  a  rubber  stopper  with  three 
perforations.  One  of  the  latter  receives  the  stem  of  a  separating 
funnel  with  a  wide  mouth  and  a  bulb  which  should  have  a  capacity 
of  about  50  cc.  ;  through  another  perforation  passes  the  \- 
inch  conduction- tube,  connecting  the  evolution  flask  directly 
under  the  stopper  with  the  absorption-tube ;  a  third  \- 
inch  tube,  the  hydrogen  tube,  passes  through  the  stopper 
to  the  bottom  of  the  flask  where  it  is  drawn  out  to  a  point  and 
bent  upwards  about  \  of  an  inch.  Above  the  stopper  it  is  con- 
nected with  a  supply  of  hydrogen. 

The  conduction-tube,  which  is  in  one  piece,  rises  perpendicu- 
larly to  about  \  inch  from  the  stopper,  bends  away  from 
the  perpendicular  about  60°,  extending  in  this  direction  5  or 
6  inches,  when  it  dips  directly  downward  into  the  absorption- 
tube,  a  10-inch  by  i-inch  lipped  test-tube  of  stout  glass.  Between 
the  first  and  second  bends  in  the  conduction-tube  are  blown  two 
f-inch  bulbs. 

The  evolution  flask  and  absorption-tube  are  securely  held  in 
the  required  position  by  specially  adapted  racks — the  flasks  over 
Argand  gas  burners — during  the  precipitation  of  the  sulphur. 

In  carrying  out  a  determination  with  tl*e  above  apparatus,  3 
to  5  grams  of  the  sample  are  placed  in  t  le  flask,  and  about  50 
cc.  of  cadmium  chloride  solution  (80  grains  of  cadmium  chlo- 


Black  Diamond  Steel  Works.  31 

ride  dissolved  in  1.5  liters  of  concentrated  ammonia  water  and 
2.5  liters  of  water)  in  the  absorption-tube.  Connections  being 
made  and  the  hydrogen  tube  closed,  50  cc.  of  dilute  hydrochloric 
acid  ( i  :  i )  are  gradually  or  at  once,  according  to  the  probable 
rate  of  evolution  of  gas,  run  into  the  flask  through  the  separa- 
ting funnel,  and  a  brisk  generation  of  gas  is  maintained,  if 
necessary,  by  the  aid  of  heat.  When  the  sample  has  dissolved, 
hydrogen  is  turned  on  in  a  slow  stream,  and  the  solution  boiled 
until  the  bulbs  of  the  conduction-tube  become  hot.  The  flame 
under  the  flask  is  then  turned  out,  and  the  passing  of  hydrogen 
continued  moderately  from  ten  to  fifteen  minutes. 

The  precipitated  cadmium  sulphide  is  next  transferred  to  a 
rapid  German  filter.  To  this  end,  after  disconnecting  the  ab- 
sorption apparatus  from  the  flask,  the  conduction-tube  is  with- 
drawn from  the  absorption-tube  and  laid  aside,  the  adhering  pre- 
cipitate being  beforehand  washed  down  into  the  tube  as  com- 
pletely as  possible  ;  the  portion  adhering  firmly  to  the  latter,  un- 
less it  be  considerable,  is  not  removed  to  the  filter,  but  left  to  be 
dissolved  off,  together  with  that  remaining  on  the  conduction- 
tube,  at  the  final  solution  of  the  precipitate.  After  several 
washings  the  filter  and  precipitate  are  placed  in  a  6oo-cc. 
beaker.  According  to  the  quantity  of  precipitate,  200—400  cc. 
of  water  are  poured  over  it,  3  cc.  of  starch  solution  (i  :  150) 
added,  and  the  mixture  stirred  until  the  filter  and  precipitate 
are  well  disintegrated. 

Fifty  cc.  of  dilute  hydrochloric  acid  (i  :  i)  are  poured  into 
the  absorption-tube,  and  water  is  added  to  fill  the  tube  to  within 
about  an  inch  of  the  top.  The  conduction-tube,  which  had 
been  laid  aside  before  the  filtration,  is  quickly  dipped  into  the 
diluted  acid  until  its  tip  nearly  touches  the  bottom,  then  raised 
and  lowered  in  the  liquid  several  times.  By  manipulating  in 
this  way,  the  precipitate  left  in  the  absorption-  and  conduction- 
tubes  is  almost  instantly  dissolved,  the  hydrogen  sulphide 
formed  absorbed  in  the  surrounding  liquid,  and  the  comparatively 
strong  solution  of  hydrogen  sulphide,  existing  on  their  surfaces 
immediately  after  the  contact  of  the  precipitate  with  the  acid, 
rinsed  off.  The  contents  of  the  absorption-tube  are  added  to  the 
water  and  precipitate  in  the  beaker.  The  precipitate  dissolves 


32  Edward  S.  Johnson. 

mainly  at  once  and  entirely  on  stirring.  Without  waiting  until 
all  cadmium  sulphide  has  dissolved,  the  estimation  of  the  sul- 
phur is  at  once  begun  by  titration  of  the  liberated  hydrogen  sul- 
phide with  iodine  solution. 

The  standard  iodine  solution  is  prepared  by  dissolving  i  gram 
of  resublimed  iodine  in  50  cc.  of  an  aqueous  solution  of  potas- 
sium iodide  (i  :  10),  and  diluting  to  i  liter.  While  pure  re- 
agents and  careful  manipulation  insure  a  solution  of  the  desired 
strength,  the  latter  is  nevertheless  confirmed  by  direct  experi- 
ment before  the  solution  is  used.  For  this  purpose  sodium  thio- 
sulphate  is  applied.  A  preparation  of  the  salt  of  requisite  purity 
may  be  made  by  recrystallization  of  the  chemically  pure  prepa- 
ration of  the  trade.  A  saturated,  warm  aqueous  solution  is  pre- 
pared and  cooled  to  nearly  o°  C.  with  constant  stirring.  The 
compound  separates  under  these  circumstances  as  a  minutely 
crystalline  mass.  By  decantation  and  the  use  of  the  filter-pump, 
the  mother-liquor  may  be  almost  completely  removed.  The  still 
moist  preparation  is  perfectly  freed  from  water  of  solution  be- 
tween sheets  of  filter-paper. 

3.  Phosphorus.  This  element  is  determined  by  weighing  as 
ammonium  phosphomolybdate. 

1.63  grams  of  steel  are  dissolved  in  a  covered  beaker  in  45  cc. 
of  20  per  cent,  nitric  acid,  the  action  of  the  acid  being  hastened 
by  warming.  When  a  perfect  solution  has  been  obtained  and 
brought  to  the  boiling-point,  an  excess  of  a  saturated  solution  of 
potassium  permanganate  is  added  and  the  boiling  continued  for 
two  or  three  minutes.  While  still  boiling,  the  mixture  is 
treated  with  sufficient  ferrous  sulphate  in  saturated,  slightly  acidi- 
fied (5  cc.  sulphuric  acid  per  liter)  solution  to  dissolve  the  pre- 
cipitated manganese  dioxide  resulting  from  the  action  of  potas- 
sium permanganate  on  the  original  nitric  acid  solution  of  the 
metal.  The  dioxide  disappears,  leaving  usually  a  clear  solu- 
tion. If  it  should  not,  recourse  must  be  had  to  filtration  for  the 
removal  of  the  "scale,"  etc.,  sometimes  unavoidably  weighed 
off  at  the  beginning  of  the  determination.  A  clear  solution  hav- 
ing been  produced,  about  15  cc.  of  water  are  added,  and  the  con- 
tents of  the  beaker  again  heated  to  boiling.  The  source  of 
heat  is  removed,  and  the  cover  and  walls  of  the  beaker  are  rinsed 


Black  Diamond  Steel   Works.  33 

down  with  water.  The  volume  of  the  liquid  at  this  stage  of  the 
operation  should  be  about  60  cc.  After  stirring  a  few  seconds, 
the  temperature  for  precipitation,  under  80°  C.,  will  exist  in  the 
solution.  45-50  cc.  of  molybdate  solution  are  then  added,  and 
the  mixture  thoroughly  and  repeatedly  stirred.  The  precipitant 
is  prepared  by  dissolving  185  grams  of  pure  ignited  "  molybdic 
acid"  in  900  cc.  of  ammonia  water  (sp.  gr.  0.96),  adding  this 
solution  to  2,700  cc.  of  32  per  cent,  nitric  acid,  and  diluting  the 
whole  with  water  to  4  liters.  The  supernatant  liquid  is  poured, 
with  as  little  disturbance  of  the  precipitate  as  possible,  when  it 
has  become  clear,  through  a  washed  Swedish  filter.  The  latter 
is  washed  twenty-five  times  with  i  per  cent,  (by  volume)  nitric 
acid,  when  the  precipitate  is  transferred  to  the  filter,  and  the 
washing  continued  until  the  precipitate  and  filter  are  free  from 
iron.  The  filter  with  its  contents  is  dried  for  one  hour  at  100° 
C.,  and  weighed  between  accurately-ground  watch-glasses,  the 
drying  and  weighing  of  the  filter  alone  having  before  been  con- 
ducted under  similar  conditions.  The  number  expressing  the 
weight  of  the  precipitate  in  grams  also  represents  the  percentage 
of  phosphorus. 

4.  Manganese. — In  the  determination  of  manganese,  the 
colorimetric  method  is  used  almost  exclusively,  the  quantities 
encountered  rarely  exceeding  3  per  cent.  For  higher  per- 
centages, as  in  the  case  of  ores  also,  a  gravimetric  method  is 
used.  For  the  latter,  see  p.  25,  Gravimetric  Method. 

COLORIMETRIC  METHOD  FOR  MANGANESE. 

The  process  consists  in  converting  the  manganese  present  into 
permanganic  acid  and  deriving  colori metrically,  by  means  of  a 
solution  of  potassium  permanganate1  containing  a  known  quan- 
tity of  manganese,  the  amount  of  manganese  in  the  permanganic 
acid  obtained  from  a  given  weight  of  steel. 

o.i  gram  of  metal  is  dissolved  in  a  lo-inch  by  i-inch  test- 
tube  in  35-40  cc.  of  32  per  cent,  nitric  acid,  and  the  solution 
heated  to  boiling  over  a  small  flame  from  a  Bunsen  burner. 
When  the  formation  of  nitrous  fumes  ceases,  the  heat  is  re- 

i  The  use  of  potassium  permanganate  in  this  connection  was,  I  believe,  first  sug- 
gested by  Mr.  B.  B.  Wright,  formerly  chemist  to  the  Black  Diamond  Steel  Works. 


34  Edward  S.  Johnson. 

moved,  and  0.2  to  0.5  gram  of  lead  peroxide  are  added.  Heat 
is  again  applied,  and  the  mixture  boiled  for  three  or  four 
minutes.  The  tube  is  then  stood  aside,  closely  covered,  and  in 
the  dark,  in  cold  water  until  the  excess  of  lead  peroxide  has 
settled  down.  When  clear,  the  acid  solution  above  the  lead  per- 
oxide— now  containing  the  manganese  as  permanganic  acid — 
is  decanted  into  a  5o-cc.  comparing  tube,  which  is  graduated  to 
0.5  cc.,  and  is  one  of  a  set  of  three  exactly  similar  tubes;  the 
remaining  two  receive  the  solutions  of  potassium  permanganate 
to  be  used  in  determining  the  quantity  of  manganese,  in  the 
form  of  permanganic  acid,  obtained  by  the  process  just  de- 
scribed. 

The  permanganate  solutions  are  prepared  from  a  stock  solu- 
tion of  such  strength  that  10  cc.  of  the  same,  when  diluted  to  250 
cc.,will  produce  a  solution  of  which  i  cc.  contains  o.ooooi  gram 
of  manganese  as  permanganic  acid.  In  practice  this  dilute  solu- 
tion is  called  the  normal  standard.  From  the  normal,  others  are 
prepared  (by  dilution  with  water  in  the  comparing  tubes)  hav- 
ing a  simple  ratio — i  12,1:3,3:4,  etc. — to  the  normal.  All  of 
these  solutions  are  adjusted  directly  before  use  from  the  stock 
solution.  The  latter  is  made  i  liter  at  a  time,  and  may,  with 
proper  precautions,  be  kept  for  several  weeks  without  apprecia- 
ble change. 

Equipped  with  this  solution  and  its  derivatives,  the  procedure 
in  estimating  the  quantity  of  manganese  in  the  permanganic 
solution,  yielded  by  a  sample  of  steel  under  the  conditions  above 
detailed,  is  obvious  and  simple.  In  one  of  the  comparing  tubes 
are  placed  30-40  cc.  of  a  standard  permanganate  solution  of 
lighter  tint  than  the  permanganic  solution.  The  latter  is  then 
diluted  with  water  until  the  tints  in  both  tubes  cannot  be  dis- 
tinguished one  from  another,  the  examination  or  "  comparing" 
of  the  shades  of  color  being  carried  out  over  a  sheet  of  white 
paper  in  the  diffuse  light  of  a  window.  The  ratio  of  the  volumes 
of  the  two  solutions  is  plainly  equal  to  the  ratio  of  the  quantity 
of  manganese  contained  in  them.  The  volumes  being  read  off 
from  the  graduated  comparing  tubes,  and  the  quantity  of  man- 
ganese in  one  solution  being  known,  the  quantity  in  the  other  is 
readily  calculated.  If  the  normal  permanganate  be  used,  the 


Black  Diamond  Steel  Works.  35 

number  expressing  the  volume  of  the  solution  (in  cubic  centime- 
ters) containing  the  unknown  quantity  of  manganese  divided  by 
100  is  the  required  percentage  when  o.i  gram  of  steel  is  taken 
for  the  determination  ;  if  a  standard  of  lighter  tint  be  used,  the 
volume  must  first  be  multiplied  by  the  fraction  showing  its  rela- 
tion to  the  normal.  For  example,  a  volume  of  35  cc.  with  the 
normal  standard  represents  0.35  per  cent,  manganese  ;  with 
a  3  :  4  standard,  0.26  per  cent. 

In  the  case  of  the  higher  percentages  of  manganese,  which  may 
still  be  determined  colorimetrically  with  convenience  and  accu- 
racy, some  modifications  of  the  general  method  already  given 
are  advisable  or  necessary.  It  is  advisable  to  weigh  off  for  the 
determination  at  least  one  gram  of  borings  that  a  representative 
result  may  be  obtained  from  the  sample.  A  solution  in  32  per 
cent,  nitric  acid  is  prepared  and  diluted  in  a  5OO-cc.  flask  to  the 
mark.  Aliquot  parts  equivalent  to  0.05  to  o.i  gram  are  then 
taken .  for  single  determinations.  After  evaporation  to  5  to  10 
cc.,  transfer  to  a  test-tube,  and  dilute  to  about  80  cc.  with  32  per 
cent,  nitric  acid,  when  the  solution  will  be  ready  for  oxidation. 
Experiments  thus  far  have  shown  that  under  the  above  conditions 
ten  to  twenty  minutes  boiling  with  0.5  gram  of  peroxide 
suffices  to  oxidize  at  least  2.5  per  cent,  manganese  in  y1^  of  a 
gram.  The  test  of  complete  oxidation  is  made  the  obtaining, 
within  the  limits  of  error,  of  the  same  result,  whether  o.i 
gram  or  half  that  quantity  be  used  for  the  determination,  the 
conditions  being  in  each  case  in  all  other  respects  the  same. 

Further,  after  the  decantation  of  the  permanganic  solution,  a 
slightly  varying  quantity  of  the  latter  is  left  adhering  to  the 
tube  and  the  residue  of  peroxide.  When  higher  percentages 
are  concerned,  the  quantity  of  manganese  represented  by  the 
liquid  residue  is  not  inconsiderable,  and  cannot  be  neglected  in 
accurate  determinations,  as  in  the  case  of  the  lower  percentages. 
The  tube  and  residual  peroxide  should  therefore  be  rinsed  with 
a  few  cubic  centimeters  of  water  or  32  per  cent,  nitric  acid.  The 
rinsings  are  filtered  through  carefully  washed  asbestos  into 
the  decanted  solution.  The  asbestos  for  the  filtration  is  pre- 
pared by  boiling  with  strong  hydrochloric  acid,  washing  with 
water,  and  ignition. 


VI.  METHODS  USED  AT  THE  LABORATORY  OF  THE 

OLIVER   &   SNYDER   STEEL  WORKS, 

PITTSBURG,  PA. 

BY  S.  M.  RODGERS. 


DETERMINATION    OF   SILICON    IN    PIG    IRON   AND    STEEL. 

i  gram  of  pig  iron,  carefully  separated  with  a  magnet,  is 
placed  in  a  4-inch  evaporating  dish  and  30  cc.  of  nitrosulphuric 
acid,  made  by  adding  60  cc.  of  concentrated  sulphuric  acid  to 
600  cc.  of  nitric  acid  (sp.  gr.  1.20),  are  added.  Cover  with  a 
watch-glass  and  place  over  a  small  flame.  When  the  solution 
of  the  drillings  is  complete,  remove  the  cover  and  rinse  into  the 
dish  with  water  and  continue  the  evaporation  cautiously,  until 
sulphuric  acid  fumes  appear.  Remove  the  dish  from  the  heat, 
cool,  add  15  cc.  of  concentrated  hydrochloric  acid,  and  10  cc.  of 
water  and  boil  till  all  the  sulphate  of  iron  is  dissolved.  Dilute 
with  an  equal  volume  of  cold  water  and  filter  through  an  ashless 
filter,  using  the  filter-pump.  Wash,  first  with  cold  water,  then 
alternately  with  cold  water  and  hot  dilute  hydrochloric  acid 
(sp.  gr.  i.io),  and  finally  with  hot  water.  Place  the  filter  and 
contents  in  a  platinum  crucible  and  burn  the  filter-paper  at  a 
low  temperature,  finishing  with  the  blast  or  muffle  till  the  pre- 
cipitate of  silica  is  perfectly  white.  If  colored  red,  add  three 
drops  of  sulphuric  acid  and  5  to  15  drops  of  hydrofluoric  acid  and 
heat  cautiously  under  the  hood  to  dryness  ;  then  use  the  blast 
till  the  iron  is  completely  oxidixed.  Cool  in  a  desiccator  and 
weigh.  The  difference  between  the  last  two  weights  is  the 
exact  weight  of  the  silica.  Should  the  sample  contain  chro- 
mium, correct  results  can  best  be  obtained  by  fusing  the  impure 
silica  with  about  2  grams  of  pure  potassium  bisulphate,  and 
heating  cautiously  till  white  fumes  of  sulphur  trioxide  are  given 
off.  Cool,  dissolve  the  mass  in  dilute  hydrochloric  acid,  filter 
off  the  purified  silica;  treat  as  in  the  first  operation,  and  cal- 
culate in  the  usual  manner. 

In  steel,  2  to  5  grams  are  dissolved  in  30  to  60  cc.  of  concen- 


Oliver  &  Snyder  Steel   Works.  37 

trated  hydrochloric  acid  and  treated  in  the  same  manner  as  pig 
iron. 

DETERMINATION  OF   SILICON  IN    FERRO-SILICON  AND 
SILICO-SPIEGEL. 

0.5  gram  of  the  finely  pulverized  sample  are  placed  in  a  4-inch 
evaporating  dish  and  50  cc.  of  dilute  hydrochloric  acid,1  made 
by  using  three  volumes  of  water  to  one  volume  of  concentrated 
acid,  are  added.  Cover  with  an  inverted  watch-glass  just  large 
enough  to  drop  inside  of  the  dish.  Place  over  a  small  flame, 
and  evaporate  to  dryness.  Follow  the  directions  given  for  the 
determination  of  silicon  in  pig  iron,  and  purify  with  hydrofluoric 
and  sulphuric  acids.  Hydrofluoric  acid  is  very  conveniently 
handled,  by  cutting  a  light  groove  in  the  inside  of  the  neck  of 
the  bottle,  beginning  below  the  termination  of  the  stopper  and 
extending  upward  a  little  more  than  half  way  to  the  top.  Then 
cut  a  similar  groove  in  the  stopper,  beginning  a  little  below  the 
termination  of  the  groove  in  the  neck  and  extend  same  to  the 
upper  end  of  the  stopper.  When  the  grooves  are  communicating, 
one  drop  at  a  time  can  be  added.  To  close  the  orifice,  the  stop- 
per is  slightly  turned  so  that  the  grooves  are  no  longer  com- 
municating. 

DETERMINATION    OF   SULPHUR    IN    IRON    AND    STEEL. 

Aqua  Regia  Method. — Weigh,  into  an  8-oz.  beaker,  6  grams  of 
iron  or  steel,  cover  with  a  watch-glass  and  add  10  cc.  of  bromine 
water,  and  60  cc.  of  aqua  regia,  a  little  at  a  time.  After  the 
violent  action  of  the  acid  has  ceased,  place  the  beaker  over  a  small 
flame  till  solution  of  the  drillings  is  complete.  Then  evaporate 
rapidly  till  the  excess  of  acid  is  expelled.  Dilute  to  120  cc. 
with  cold  water,  mix  thoroughly  and  filter  exactly  100  cc.  (the 
equivalent  of  five  grams),  add  5  cc.  of  a  saturated  solution  of 
citric  acid,  and  10  cc.  of  a  10  per  cent,  solution  of  barium 
chloride.  Stir  occasionally  and  set  aside  over  night.  Care- 
fully decant  the  clear  supernatant  liquid  into  a  platinum  Gooch 
crucible,  containing  an  accurately-fitting  disk  of  filter-paper, 
using  moderate  suction.  Discard  the  clear  filtrate,  and  detach 

l  The  formula  for  mixing  this  solvent  was  first  obtained  from  Mr.  C.  B.  Murray,  of 
Edgar  Thompson  Steel  Works,  Braddock,  Pa. 


38  5.  M.  Rodgers. 

from  the  pump.  Now  transfer  the  entire  precipitate  to  the  filter 
and  wash  with  a  dilute  solution  of  hot  hydrochloric  acid,  using 
a  few  drops  of  hydrofluoric  acid  to  dissolve  any  silica  that  may 
have  been  carried  down  with  the  precipitate,  continue  the  wash- 
ing till  the  precipitate  is  entirety  free  from  iron  salts,  and  lastly 
use  a  little  hot  water.  Place  the  cap  on  the  crucible  and  dry 
over  a  small  flame.  Then  burn  off  the  carbon  completely,  cool 
in  a  desiccator,  and  weigh.  Multiply  the  weight  of  barium 
sulphate  by  13.7  and  divide  by  5.  The  result  will  be  the  per 
cent,  of  sulphur  in  the  sample. 

Evolution  Method. — 5  grams  of  iron  or  steel  are  placed  in  a  16- 
oz.  ring-neck  flask,  carrying  a  4-oz.  funnel-tube  and  a  delivery- 
tube,  the  latter  terminating  at  the  bottom  of  an  8- inch  test-tube 
containing  a  solution  of  ammoniacal  cadmium  chloride.  4  oz. 
of  hydrochloric  acid  (sp.  gr.  i.io)  are  placed  in  the  funnel- 
tube  and  allowed  to  flow  into  the  flask.  After  the  violent  action 
of  the  acid  has  ceased,  place  the  flask  over  a  small  flame  and 
continue  the  evolution  till  the  drill  ings  are  completely  dissolved. 
Finally  bring  the  solution  to  a  boil  for  about  two  or  three 
minutes.  Disconnect  the  flask  and  remove  from  the  heat. 
Transfer  the  contents  of  the  tube  to  a  white  bowl  and  dilute 
with  200  cc.  of  cold  water.  Acidulate  with  hydrochloric  acid 
by  conducting  it  through  a  tube  to  the  bottom  of  the  solution. 
Add  3  cc.  of  starch  solution  and  titrate  with  standard  solution 
of  iodine,  i  cc.  of  which  is  equivalent  to  o.oi  per  cent,  of  sul- 
phur in  5  grams  of  the  sample,  thus  obviating  the  necessity  for 
a  calculation. 

The  iodine  solution  is  made  by  dissolving  4  grams  of  resub- 
limed  iodine  in  8  grams  of  pure  potassium  iodide  dissolved  in 
10  cc.  of  water,  and  diluted  to  one  liter,  which  makes  approxi- 
mately the  strength  desired.  The  solution  is  then  accurately 
standardized  by  running  the  iodine  solution  against  an  exact 
weight  of  sodium  thiosulphate,  this  weight  having  been  pre- 
viously determined,  by  first  accurately  standardizing  the  iodine 
solution  by  the  bichromate  and  thiosulphate  method,  and  then 
carefully  determining,  by  numerous  experiments,  the  exact 
weight  of  sodium  thiosulphate  equivalent  to  the  iodine.  This 
having  been  done  on  a  large  quantity  of  the  thiosulphate  and 


Oliver  &  Snyder  Steel  Works.  39 

the  weight  noted  on  the  container,  makes  the  work  of  standard- 
izing iodine  both  accurate  and  rapid. 

DETERMINATION    OF   PHOSPHORUS    IN    PIG    IRON   AND  STEEL. 

Weigh  into  a  6-oz.  casserole  1.63  grams  of  drillings,  and 
cover  with  an  inverted  watch-glass  just  large  enough  to  drop 
inside  of  the  dish.  Add  50  cc.  of  nitric  acid  (sp.  gr.  1.20),  and  place 
over  a  small  flame;  when  solution  is  complete,  evaporate  rapidly 
to  dryness.  Then  increase  the  heat  till  the  bottom  of  the  dish  is  a 
dull  red,  and  continue  this  heat  till  oxidation  of  the  organic 
matter  and  phosphorus  is  complete,  which  may  be  indicated  by 
holding  the  wet  stopper  of  the  ammonia  bottle  within  the 
dish.  The  absence  of  white  fumes  indicates  that  this  stage  of 
the  process  is  completed.  The  watch-glass  need  not  be  removed 
if  care  be  taken  not  to  cool  the  dish  too  rapidly.  When  cold,  dis- 
solve the  mass  in  15  cc.  of  a  mixture  of  390  cc.  concentrated 
hydrochloric  acid  and  60  cc.  concentrated  sulphuric  acid. 
Evaporate  till  the  mass  has  the  appearance  of  burnt  sugar,  or 
almost  to  dryness.  Now  add,  drop  by  drop  without  cooling,  10 
cc.  hot  dilute  hydrochloric  acid,  and  sufficient  water  to  effect 
complete  solution  of  the  mass,  concentrate,  add  10  cc.  strong 
nitric  acid,  and  boil  till  the  red  fumes  pass  off.  Dilute  with  25 
cc.  of  cold  water,  and  filter  under  strong  suction.  Wash  first 
with  cold  water,  then  with  a  few  drops  of  hot  hydrochloric  acid, 
and  then  with  hot  water.  To  the  filtrate  add  10  cc.  of  strong 
ammonia,  and  then  just  enough  strong  nitric  acid  to  dissolve  the 
precipitated  iron  and  render  the  solution  a  deep  amber  color. 
Heat  or  cool  to  exactly  80°  C.,  add  40  cc.  of  molybdic  acid  solu- 
tion, and  shake.  Set  in  a  warm  place  till  the  precipitate  settles, 
which  should  not  be  more  than  fifteen  to  thirty  minutes. 

Filter  through  a  Gooch  crucible  containing  an  accurately-fit- 
ting disk  of  No.  o  Swedish  filter-paper,  using  strong  suction.  The 
precipitate  will  not  run  through  if  the  solution,  before  precipita- 
tion, is  not  too  strongly  acid.  Otherwise  it  invariably  runs 
through.  The  precipitate  is  thoroughly  washed  with  a  solution 
of  2.5  per  cent,  hydrochloric  acid  and  2.5  percent,  molybdic  acid 
solution.  The  crucible  and  contents  are  transferred  to  the  hot 
air-bath  and  dried  at  120°  C.  Or  the  precipitate  may  be 


40  6*.  M.  Rodger s. 

thoroughly'  dried  in  three  minutes  by  drawing  clean,  dry,  hot 
air  through  the  crucible.  If  the  disks  are  cut  from  carefully 
selected  filter-paper,  they  will  not  vary  in  weight  more  than  i 
milligram,  and  by  noting  this  we  can  eliminate  one  weight  in 
each  determination.  The  solvent  action  of  the  solutions  do  not 
appreciably  affect  the  weight  of  the  paper  disk  as  might  be  the 
case  in  using  a  whole  filter. 

If  extreme  accuracy  be  required,  the  precipitate  may  be  dis- 
solved off  the  disk  with  ammonia,  neutralized  with  hydrochloric 
acid  and  let  stand  over  night.  Any  iron  or  silica  that  may  have 
been  retained  by  the  precipitate  can  be  estimated  by  filtering 
through  the  same  disk,  washed,  dried,  and  weighed.  On  subtract- 
ing this  result  from  the  previous  weight,  the  difference  between 
the  two  weights  in  milligrams,  will  be  the  per  cent,  of  phos- 
phorus in  the  sample. 

In  checking  all  results,  the  molybdate-magnesia  method  is 
used  mainly,  as  described  by  Prof.  N.  W.  Lord  in  his  "  Notes 
on  Metallurgical  Analysis,"  p.  22. 

DETERMINATION   OF   MANGANESE. 

Weigh  5  grams  of  iron  or  steel  into  a  6-oz.  casserole  and  dis- 
solve in  60  cc.  of  strong  nitric  acid.  When  solution  is  complete, 
add  10  cc.  of  concentrated  hydrochloric  acid  and  boil  five  minutes. 
Filter,  if  necessary,  and  concentrate  the  filtrate  to  a  small  bulk. 
Add  25  cc.  of  strong  nitric  acid  and  5  grams  of  pure  potassium 
chlorate,  cover  with  a  watch-glass,  and  boil  ten  minutes.  Re- 
peat this  operation  once,  if  the  sample  is  low  in  manganese, 
and  twice  if  high.  Boil  fifteen  minutes  after  the  last  addition  of 
potassium  chlorate,  filter  through  an  asbestos  plug,  and  wash 
with  strong  nitric  acid.  Transfer  the  plug  and  precipitate  to 
the  same  beaker  in  which  the  precipitation  was  made,  rinsing  out 
the  last  particles  with  dilute  hydrochloric  acid,  add  a  few  crystals 
of  oxalic  acid,  dilute  with  25  cc.  of  hot  water,  and  boil  till  the 
manganese  dioxide  is  completely  dissolved.  Filter  and  wash 
thoroughly  with  hot  water,  and  boil  the  filtrate  a  few  minutes. 
Dilute  to  250  cc.,  and  cautiously  add  dilute  ammonia  water 
(i  :  i)  till  a  faint  permanent  precipitate  of  iron  is  produced;  add 
slowly  25  cc.  of  a  concentrated  solution  of  ammonium  acetate 


Oliver  &  Snyder  Steel   Works.  41 

with  constant  stirring.  Cover  the  beaker  and  boil  three  minutes; 
allow  the  precipitate  to  settle,  and  decant  the  supernatant  liquid 
through  a  filter,  letting  the  filtrate  run  into  a  24-oz.  beaker,  and 
wash  the  precipitate  once  or  twice  by  decantation .  Transfer  the 
precipitate  to  the  filter  and  wash  once  with  hot  water.  Redis- 
solve  the  precipitate  with  the  least  quantity  of  hot  dilute  hydro- 
chloric acid,  allowing  the  solution  to  run  into  the  same  beaker  in 
which  the  precipitation  was  made,  and  make  a  second  basic  ace- 
tate separation  in  the  same  manner.  Test  this  precipitate  with 
sodium  carbonate  on  a  platinum  wire,  and  if  not  free  from 
manganese,  make  a  third  separation.  Concentrate  the  filtrate 
to  about  300  cc.  and  add  5  to  10  cc.  of  acetic  acid,  boil,  and  add 
5  to  10  grams  of  ammonium  phosphate,  stirring  till  crystalline. 
Finally,  add  15  to  25  cc.  of  strong  ammonia  and  continue  the 
stirring  till  the  precipitate  is  completely  crystalline  in  its  charac- 
teristic silky  form.  Remove  from  the  heat  and  let  the  precipi- 
tate settle.  Filter  through  an  ashless  filter  and  wash  thoroughly 
with  water  containing  a  few  cubic  centimeters  of  ammonia. 
Transfer  the  precipitate  to  a  deep  platinum  crucible  and  heat 
cautiously  till  the  filter-paper  is  charred.  Then  increase  the 
heat  slowly  to  the  highest  temperature  of  the  blast,  and  con- 
tinue this  heat  till  the  precipitate  is  perfectly  white  and  constant 
in  weight.  Cool  in  a  desiccator,  weigh,  multiply  the  weight  by 
0.3874,  divide  by  the  number  of  grams  taken,  and  the  result 
will  be  the  per  cent,  of  manganese  in  the  sample. 

DETERMINATION   OF    NICKEL   IN   STEEL. 

Weigh  into  a  large  beaker  0.5  to  2  grams  of  steel,  and  dis- 
solve in  dilute  hydrochloric  acid  (sp.  gr.  1.12).  Add  10  cc. 
bromine  water  and  boil  till  iron  is  completely  oxidized.  Dilute 
to  about  400  cc.  with  water.  Precipitate  the  iron  with  concen- 
trated ammonia,  filter  rapidly  on  a  ribbed  filter,  and  wash  the 
precipitate  three  or  four  times  with  hot  water.  Suck  the  pre- 
cipitate dry,  puncture  the  filter,  and  wash  the  precipitate  into  the 
original  beaker.  Dissolve  the  last  traces  of  the  precipitate  with 
hot  dilute  hydrochloric  acid,  add  ten  cc.  strong  hydrochloric 
acid,  and,  when  solution  is  complete,  dilute  to  300  cc.  with  water 
and  precipitate  the  iron  as  before,  using  a  moderate  excess  of 


42  6*.   M.  Rodger  s, 

ammonia.  Make  at  least  four  precipitations  in  this  manner, 
using  an  excess  of  ammonia  each  time  ;  combine  the  filtrates  and 
concentrate  till  crystallization  of  the  salts  begins.  Place  on  a 
steam-bath  and  dissolve  any  separated  salts  in  25  cc.  of  strong 
ammonia.  Filter  through  a  small  filter  and  wash  with  dilute 
ammonia  water  till  the  filtrate  measures  275  cc.  in  volume. 
Precipitate  the  nickel  on  a  weighed  platinum  cylinder  which  is 
connected  with  the  zinc  plate  of  a  battery  of  2  or  3  Bunsen  cells, 
keeping  the  solution  at  80°  C. 

DETERMINATION  OF  NICKEL  AND  COBALT. 

i  to  5  grams  of  the  sample  are  placed  in  a  small  flask,  and  a 
mixture  of  5  cc.  of  concentrated  nitric  acid,  5  cc.  of  concentrated 
sulphuric  acid,  and  3  cc.  of  concentrated  hydrochloric  acid 
added  for  every  gram  of  the  sample  taken.  Heat  over  a  small 
flame  till  solution  is  complete  and  copious  fumes  of  sulphuric 
anhydride  are  given  off,  adding  more  sulphuric  acid  if  required 
to  avoid  going  to  dryness.  Cool,  dilute  with  water,  filter,  and 
wash  thoroughly  with  hot  water.  If  second  group  bases  are 
present,  the  filtrate  is  heated  to  about  70°  C.,  and  a  strong  cur- 
rent of  hydrogen  sulphide  gas  is  passed  through  the  solution  till 
the  latter  is  cold.  Filter  out  the  precipitated  sulphides,  wash 
thoroughly  with  hydrogen  sulphide  water,  and  boil  the  filtrate. 
While  boiling  add  hydrochloric  acid  and  potassium  chlorate,  a  lit- 
tle at  a  time,  till  oxidation  of  the  iron  is  complete.  Dilute  with 
water  and  add  ammonia,  stirring  constantly,  till  the  iron  is  com- 
pletely precipitated,  and  the  solution  decidedly  alkaline.  Filter 
and  wash  the  precipitate  once  or  twice  with  hot  water.  Dissolve  the 
precipitate  with  dilute  hydrochloric  acid  and  add  ammonium 
carbonate  till  a  slight  permanent  precipitate  is  produced.  Add 
one  drop  of  hydrochloric  acid  to  clear  the  solution,  then  10  to  15 
grams  of  ammonium  acetate  and  bring  to  a  boil.  Remove  from 
the  heat  a  few  minutes  till  the  precipitate  settles,  and  filter, 
using  moderate  suction.  Wash  with  hot  water,  and  dissolve 
the  precipitate  with  dilute  hot  hydrochloric  acid,  letting  the 
solution  run  into  the  original  beaker,  and  make  a  second  pre- 
cipitation in  the  same  manner  as  the  first.  Combine  the  filtrates, 
concentrate  to  350  cc.,  and  acidify  slightly  with  acetic  acid. 


Oliver  &  Snyder  Steel  Works.  43 

Boil  and  pass  a  current  of  hydrogen  sulphide  through  the  solu- 
tion while  boiling.  Filter  off  the  precipitated  sulphides  of 
nickel  and  cobalt,  and  wash  thoroughly  with  hydrogen  sulphide 
water.  Acidify  the  nitrate  slightly  with  acetic  acid  and  boil. 
If  any  further  precipitation  takes  place,  collect  on  a  filter  and 
wash  as  above.  Transfer  ,the  precipitates  from  the  filters  as 
completely  as  possible,  ignite  the  filters,  and  add  the  ashes  to 
the  precipitates  and  dissolve  the  sulphides  in  aqua  regia.  Expel 
the  excess  of  acid  by  evaporation,  dilute  with  water,  add  a  solu- 
tion of  moderately  strong  potassium  hydroxide,  and  heat  almost 
to  boiling  for  some  time.  Filter,  wash,  and  transfer  the  precipi- 
tate to  a  beaker  as  completely  as  possible,  dissolving  off  the 
last  traces  with  a  solution  of  potassium  cyanide,  receiving  the 
filtrate  in  the  beaker  containing  the  precipitate.  Warm  gently  till 
the  precipitate  is  dissolved,  and  heat  to  boiling  to  expel  excess 
of  hydrocyanic  acid.  Add  to  the  hot  solution  finely  pulverized 
mercuric  oxide  and  boil.  Filter  off  the  precipitated  nickel, 
wash,  dry,  and  ignite  in  a  weighed  porcelain  crucible.  Multiply 
the  weight  of  the  precipitate  by  0.78667  to  obtain  the  weight  of 
the  nickel,  from  which  the  per  cent,  can  be  readily  calculated. 

In  order  to  insure  accurate  results,  boil  the  oxide  in  water, 
filter,  wash,  dry,  and  ignite  as  before.  A  decrease  in  weight  is 
likely  due  to  some  adhering  salt.  Dissolve  the  nickel  in  aqua 
regia,  dilute  in  water,  and  filter  through  an  ashless  filter. 
Ignite,  weigh,  and  deduct  from  the  oxide  of  nickel.  Dilute 
the  filtrate,  add  an  excess  of  ammonia,  and  let  stand  over  night. 
If  a  precipitate  occurs,  filter,  wash,  ignite,  and  deduct  this  weight 
also  from  the  weight  of  the  nickel  oxide.  From  the  remainder, 
calculate  the  per  cent,  of  metallic  nickel. 

Carefully  neutralize  the  filtrate  from  the  precipitated  nickel 
by  mercuric  oxide,  with  nitric  acid,  and  add  a  solution  of  mer- 
curous  nitrate  as  long  as  a  precipitate  of  mercury  cobaltocya- 
nide  is  formed.  Filter,  wash,  and  dry  the  precipitate,  and  reduce 
the  cobalt  to  the  metallic  state  in  a  current  of  hydrogen  in  a 
Rose  crucible,  and  weigh. 


44  -5*-  M-  Rodger s. 

DETERMINATION  OF  CHROMIUM  IN  CHROME  ORE  AND  FERRO- 

CHROME. 

Weigh  into  a  platinum  crucible,  whose  capacity  is  not  less 
than  40  or  50  cc.,  0.5  gram  of  fine  ground  ore,  place  on  top  of  it 
25  grams  of  potassium  bisulphate,  and  fuse  very  cautiously  over 
a  very  low  flame.  After  the  mass  is  in  a  liquid  condition,  in- 
crease the  heat  cautiously  to  dull  redness.  Carefully  run  the 
fusion  up  on  the  sides  of  the  crucible  to  dislodge  any  stranded 
particles  of  ore.  The  mass  must  now  be  kept  in  a  state  of  tran- 
quil fusion  at  least  forty  or  fifty  minutes,  or  longer  if  the  sample 
has  not  been  finely  pulverized.  Cool  the  crucible,  place  it 
in  a  5-inch  casserole,  cover  the  crucible  with  hot  water,  and  in- 
vert a  watch-glass  over  the  solution  and  crucible  just  large 
enough  to  drop  inside  the  edges  of  the  dish,  Place  the  dish  in 
an  air-bath  at  i2o°C.  till  the  contents  are  readily  washed  from  the 
crucible.  Wash  off  the  watch-glass,  add  35  to4occ.  concentra- 
ted hydrochloric  acid  and  15  cc.  of  hot  water,  and  boil  gently  till 
solution  is  complete.  Remove  from  the  heat  and  let  the  silicious 
matter  settle.  Decant  the  supernatant  liquid  into  a  i2-oz. 
beaker,  add  15  or  20  cc.  more  hydrochloric  acid  to  the  resi- 
due, and  boil  gently  fifteen  minutes  longer.  Combine  the  two 
solutions  and  filter  through  an  ashless  filter,  wash,  ignite,  and 
weigh  the  silica.  The  filtrate  is  made  slightly  alkaline  with 
ammonia  and  heated  on  the  steam-bath  till  the  chromium,  iron, 
and  aluminum  are  completely  precipitated  and  the  excess  of 
ammonia  is  volatilized.  Filter  without  washing,  dissolve  the 
precipitate  in  dilute  hydrochloric  acid,  and  receive  the  fil- 
trate in  the  original  beaker.  Reprecipitate  in  the  same  manner, 
filter,  and  wash  the  precipitate  two  or  three  times  with  hot  water. 
Combine  the  two  filtrates  and  determine  the  calcium  and  mag- 
nesium by  any  good  method.  Transfer  the  precipitate  and  filter 
to  the  5-inch  casserole,  add  50  cc.  of  strong  nitric  acid,  cover 
with  a  watch-glass,  heat  gently  to  boiling,  and  add,  cautiously, 
potassium  chlorate,  little  by  little,  till  the  iron  and  chromium 
are  completely  oxidized,  which  is  indicated  by  the  deep  orange 
color  of  the  chromic  acid.  Transfer  to  a  beaker  and  dilute  to 
200  cc.  with  water.  Precipitate  the  iron  and  aluminum  with 


Oliver  &  Snyder  Steel   Works.  45 

ammonia  and  filter  into  a  24-oz.  beaker,  without  washing.  Dis- 
solve the  precipitate  with  warm,  dilute  nitric  acid,  and  receive  the 
filtrate  in  the  same  beaker  in  which  it  was  made.  Reprecipitate 
as  before  and  filter,  receiving  the  filtrate  in  the  same  beaker  as 
the  first.  Repeat  these  solutions  and  precipitations  till  the  re- 
sulting precipitate  of  iron  and  aluminum  gives  no  reaction  for 
chromium  when  a  small  part  of  it  is  fused  on  a  platinum  wire 
with  sodium  carbonate.  The  iron  and  aluminum  may  be  de- 
termined by  any  good  method.  To  the  filtrate  containing  the 
chromium,  add  acetic  acid  to  slight  acid-reaction,  and  add  locc. 
of  a  20  per  cent,  solution  of  lead  acetate.  Cover  and  set  aside  for 
about  four  hours,  stirring  frequently.  Filter  on  a  Gooch  cruci- 
ble as  in  the  determination  of  phosphorus,  and  wash  with  cold 
water  till  the  washings  give  no  reaction  for  lead  with  fresh 
hydrogen  sulphide  water.  Dry  in  an  air-bath  at  ioo°  C.  till  the 
precipitate  ceases  to  lose  weight.  If  pure,  16.181  per  cent,  of 
the  weight  is  metallic  chromium. 

DETERMINATION  OF  CARBON  IN  IRON  AND    STEEL. 

The  determination  of  carbon  is  made  according  to  the  process 
described  in  Blair's  "Chemical  Analysis  of  Iron,"  Third  Edi- 
tion, p.  148. 

DETERMINATION  OF  GRAPHITE  IN  PIG    IRON. 

i  to  3  grams  of  pig  iron  are  carefully  separated  with  a  mag- 
net and  dissolved  slowly  in  30  to  60  cc.  of  nitric  acid  (sp.  gr. 
1.13)  in  an  8-oz.  beaker.  Set  aside  till  the  graphite  settles. 
Dry  and  weigh  accurately  a  platinum  Gooch  crucible  con- 
taining an  accurately- fitting  disk  of  filter-paper.  Place  in  the 
filtering  tube,  and  filter  the  solution  through  the  crucible,  using 
strong  suction.  Wash  alternately  with  hot  dilute  hydrochloric 
acid  (sp.  gr.  i.io)  and  cold  water;  then  with  a  10  per  cent, 
solution  of  caustic  soda,  alternating  with  hot  dilute  hydrochloric 
acid  and  hot  water,  and  finally  with  much  acid  and  hot  water 
till  the  last  traces  of  soda  are  washed  out ;  and  lastly,  with 
ether.  Dry  in  an  air-bath  at  100°  C.  and  weigh.  Ignite  the 
crucible  in  the  blast  till  all  the  graphitic  carbon  is  completely 
oxidized;  cool  and  weigh.  Any  increase  in  weight  over  the 


46  Oliver  &  Snyder  Steel   Works. 

weight  of  the  empty  crucible  will  be  the  weight  of  retained 
silica.  This  subtracted  from  the  previous  weight  of  the  precipi- 
tate, will  give  the  true  weight  of  graphite. 


VII.  METHODS  USED  AT  THE  LABORATORY  OF  THE 

HAINS WORTH  STEEL  CO.,  EDITH  FURNACE 

DEPARTMENT,  ALLEGHENY,  PA. 


BY  R.  G.  JOHNSTON. 


DETERMINATION  OF  SILICA  IN  IRON  ORES. 

Weigh  out  i  gram  of  the  finely  ground  ore,  and  transfer  to  a 
platinum  crucible  containing  about  10  grams  of  sodium  carbon- 
ate. Fuse  for  about  fifteen  minutes,  or  until  a  quiet  fusion  is 
obtained.  Allow  the  crucible  to  cool,  and  place  it  in  a  beaker  con- 
taining about  40  cc.  of  water  ;  add  about  15  cc.  of  hydrochloric 
acid  to  dissolve  the  fused  mass  out  of  the  crucible.  Remove  the 
crucible,  rinsing  it  with  a  fine  jet  of  water.  Stand  the  beaker 
on  the  sand-bath,  and  evaporate  its  contents  to  dry  ness  over 
night.  Moisten  the  mass  with  a  few  cubic  centimeters  of  hydro- 
chloric acid,  and  add  about  30  cc.  of  hot  water.  When  all  has 
dissolved,  filter,  wash  well  with  hot  water,  dry,  ignite,  and 
weigh  as  SiO2. 

The  filtrate  may  be  used  for  determining  either  iron  or 
alumina. 

DETERMINATION  OF  IRON  IN  IRON  ORES. 

Weigh  off  0.5  gram  of  the  finely  ground  ore  into  a  beaker 
without  lip.  Digest  with  30  cc.  of  hydrochloric  acid  over  night 
on  the  sand-bath.  A  solution  of  stannous  chloride  is  now  added 
drop  by  drop  until  the  ferric  chloride  solution  is  completely  de- 
oxidized. Dilute  with  about  100  cc.  of  hot  water  and  add  30  cc. 
of  a  solution  of  mercuric  chloride  to  oxidize  an  excess  of  stan- 
nous chloride. 

Titrate  with  a  standard  solution  of  potassium  bichromate, 
testing  after  each  addition  of  the  standard  solution  with  a  drop 
of  potassium  ferricyanide,  on  a  white  plate,  for  ferrous  chloride. 

The  stannous  chloride  solution  is  made  by  dissolving  80  grams 
of  the  common  salt  in  500  cc.  of  water  and  an  equal  volume  of 
hydrochloric  acid. 


48  R.   G.  Johnston. 

To  prepare  the  mercuric  chloride  solution  dissolve  50  grams 
of  the  compound  in  i  liter  of  water  acidified  with  15  cc.  of  hy- 
drochloric acid. 

DETERMINATION  OF  PHOSPHORUS  IN  IRON  ORES. 

Weigh  out  5  grams  of  the  sample  (10  grams  if  very  low  in 
phosphorus)  and  digest  in  a  beaker  with  boiling  hydrochloric 
acid  for  about  one-half  hour.  Filter,  and  fuse  the  residue  with 
about  4  grams  of  sodium  carbonate.  Dissolve  the  fusion  and 
evaporate  the  two  solutions  to  dryness.  Moisten  with  a  few 
cubic  centimeters  of  hydrochloric  acid,  take  up  with  hot  water 
and  filter  from  the  silica.  Combine  the  two  filtrates,  and  evapo- 
rate to  a  syrup.  Add  about  30  cc.  of  nitric  acid  (sp.  gr.  1.42), 
and  evaporate  a  second  time  to  get  rid  of  the  last  traces  of  hy- 
drochloric acid.  Dilute  the  solution  to  about  50  cc.,  and  add  15 
cc.  of  strong  ammonia,  which  will  form  a  thick  paste.  Dissolve 
the  latter  in  about  30  cc.  of  nitric  acid  (sp.  gr.  1.20).  Heat  the 
solution  to  80°  C.,  and  add  100  cc.  of  molybdic  acid  solution. 
Stir  for  a  few  minutes  and  allow  the  precipitate  to  settle.  After 
about  one  hour,  filter,  and  wash  with  a  one  per  cent,  solution  of 
nitric  acid .  Dissolve  the  precipitate  on  the  filter  with  a  solution 
of  ammonia  (i  :  2),  allowing  the  solution  to  run  into  a  small 
beaker  containing  a  few  crystals  of  citric  acid  and  about  3  cc.  of 
hydrochloric  acid.  The  volume  of  the  solution  should  now  be 
about  100  cc.  Add  a  few  cubic  centimeters  of  magnesia  solu- 
tion, stir  well,  and  allow  the  mixture  to  stand  over  night.  Fil- 
ter and  wash  well  with  the  above  ammonia  solution.  Dry, 
ignite,  and  weigh.  Dissolve  the  precipitate  in  the  crucible  in 
about  5  cc.  of  water  and  3  cc.  of  nitric  acid,  and  determine  the 
weight  of  any  residue  insoluble  in  the  acid.  Deduct  from  the 
weight  of  the  precipitate  as  obtained  above.  The  difference  is 
the  weight  of  magnesium  pyrophosphate  derived  from  phosphate 
in  the  ore. 

I  have  used  this  method  for  some  three  years  and  have  always 
had  good  results. 

DETERMINATION  OP  MANGANESE    IN    PIG  IRON    AND    IRON  ORE. 

Weigh  out  2  grams  of  the  iron  and  dissolve  in  40  cc.  of  nitric 


Hainsworth  Steel  Company.  49 

acid  (sp.  gr.  1.20).  In  a  porcelain  dish,  3.5  inches  in  di- 
ameter, evaporate  to  a  syrup  or  until  a  further  evaporation 
would  cause  iron  to  separate  out  as  basic  nitrate.  Dilute  and 
wash  into  a  half-liter  flask  ;  neutralize,  and  precipitate  with  ox- 
ide of  zinc.  Make  the  solution  up  to  the  mark,  and  shake  well. 
Allow  the  precipitate  to  settle  in  a  large  beaker,  decant  off  250 
cc.  of  the  solution  which  correspond  to  i  gram  of  iron,  transfer 
to  a  flask,  and  heat  to  boiling.  Titrate  with  a  solution  of  potas- 
sium permanganate,  shaking  well  after  each  addition  of  the 
standard  solution.  A  pink  coloration  will  show  the  end  of  the 
reaction. 

For  iron  ores  low  in  manganese,  dissolve  in  hydrochloric  acid 
of  1.20  sp.  gr.  If  a  hematite,  add  a  few  drops  of  nitric  acid  of 
i. 20  sp.  gr.  Magnetite  will  require  more  oxidizing  agent.  In 
other  respects  proceed  as  above. 

DETERMINATION  OF  SILICON  IN  PIG  IRON. 

Ford's  method  is  used  for  this  determination.  See  Blair's 
"  Chemical  Analysis  of  Iron,"  Third  Edition,  p.  77. 

DETERMINATION  OF  SULPHUR  IN  PIG  IRON. 

In  determining  sulphur,  the  evolution  method  is  used.  The 
hydrogen  sulphide  formed  in  dissolving  the  sample  is  absorbed 
in  a  solution  of  caustic  soda  (i  :  8),  and,  after  acidification  of 
the  absorbent,  titrated  with  iodine  solution. 

DETERMINATION  OF  PHOSPHORUS  IN  PIG  IRON. 

Kmmerton's  method  as  described  by  Blair's  "Chemical  Analy- 
sis of  Iron,"  Second  Edition,  p.  95,  is  made  use  of. 

DETERMINATION  OF  MANGANESE  IN  PIG  IRON. 

The  method  of  Volhard  as  modified  by  O.  Textor  is  used  for 
the  estimation  of  manganese.  The  details  have  already  been 
given  in  the  description  of  methods  for  the  analysis  of  ores. 


VIII.  METHODS  USED  AT  THE  LABORATORY  OF 

THE  CARNEGIE  STEEL  CO.,  EDGAR  THOMSON 

STEEL  WORKS  AND  FURNACES, 

BRADDOCK,  PA. 

'BY  C.  B.  MURRAY. 


DETERMINATION  OF  SILICA  IN  IRON  ORES. 

i  gram  of  the  dried  ore  is  fused  with  12  to  15  grams  of  sodium 
carbonate  in  a  large  platinum  crucible.  After  thorough  fusion 
the  crucible  and  contents  are  cooled  in  a  i2-oz.  beaker  contain- 
ing about  200  cc.  of  water.  About  the  same  volume  of  strong 
hydrochloric  acid  is  now  added  and  the  fusion  is  dissolved.  The 
solution  is  evaporated  to  dry  ness  on  a  steam  table,  the  residue 
taken  up  with  50  cc.  hydrochloric  acid  diluted  with  water,  the 
silica  filtered,  ignited,  and  weighed. 

In  the  case  of  manganese  ores,  i  gram  of  the  ore  is  dissolved 
in  50  cc.  hydrochloric  acid,  boiled,  filtered,  and  the  residue 
fused.  The  fusion  is  added  to  the  original  solution.  Then  pro- 
ceed as  above.  This  is  to  avoid  the  action  of  chlorine  on  the 
crucible. 

DETERMINATION  OF  IRON  IN  ORES. 

0.5  gram  of  the  ore  is  dissolved  in  50  cc.  hydrochloric  acid. 
In  case  the  residue  left  is  not  white  the  solution  is  filtered,  the 
residue  fused  with  sodium  carbonate,  dissolved  out  in  hydro- 
chloric acid,  the  iron  precipitated  as  hydroxide,  dissolved  in 
dilute  hydrochloric  acid  (i  :  i),  and  the  solution  added  to  main 
solution.  As  a  rule  there  is  no  iron  left  in  the  residue,  and  then 
a  fusion  is  not  necessary. 

To  the  hot  solution  of  the  ore,  stannous  chloride  is  added  from 
a  burette  drop  by  drop,  stirring  all  the  while,  till  the  solution  is 
colorless.  Three  drops  in  excess  are  then  added.  After  allow- 
ing a  few  minutes  for  the  stannous  chloride  to  complete  the  re- 
duction of  any  iron  adhering  to  the  silica,  dilute  to  about  400 
cc.  with  cold  water,  add  all  at  once  20  cc.  mercuric  chloride  solu- 
tion, and  stir  vigorously.  Now  add  from  a  burette  potassium 


Edgar  Thomson  Steel  Works  and  Furnaces.  51 

bichromate  enough  to  nearly  oxidize  all  the  iron.  Place  on  a 
white  tile  several  drops  of  the  ferricyanide  solution.  Take  out 
a  drop  of  solution  from  the  beaker  and  let  it  fall  into  a  drop  of 
the  ferricyanide.  Continue  adding  bichromate  and  testing  as 
above  till  blue  color  is  faint.  Then  take  two  drops  for  every 
test.  Wait  one-half  minute  at  each  test  for  color  to  develop. 
When  no  blue  color  appears  at  the  end  of  one-half  minute,  take 
the  burette  reading,  which  gives  directly  the  percentage  of  iron 
in  the  ore. 

SOLUTIONS  EMPLOYED. 

The  potassium  dichromate  solution  contains  4.4  grams  of  the 
salt  in  i  liter  of  water. 

i  cc.  corresponds  to  0.005  gram  iron,  or  to  i  per  cent,  when 
0.5  gram  of  ore  is  employed. 

The  mercuric  chloride  solution  contains  50  grams  of  the  salt 
in  i  liter. 

The  stannous  chloride  solution  contains  50  grams  in  i  liter. 

The  potassium  ferricyanide  solution  contains  two  or  three 
pieces  of  the  size  of  pin  heads  in  50  cc.  of  water.  Prepare  every 
other  day. 

DETERMINATION  OF  PHOSPHORUS  IN  ORES. 

Dissolve  10  grams  of  the  ore  when  the  phosphorus  is  under 
0.070  per  cent.,  or  5  grams  when  it  is  above  0.070,  in  150  cc. 
hydrochloric  acid.  Filter  by  suction.  Treat  the  residue  in  the 
same  manner  as  for  silica  and  evaporate  main  solution  to  dryness 
on  the  steam  table.  Take  up  main  solution  and  fusion  of  resi- 
due each  with  100  cc.  nitric  acid.  Heat  on  the  sand-bath  till 
all  is  in  solution.  Filter  and  unite  the  filtrates.  To  this  liquid, 
which  should  not  exceed  300  cc.,  add  ammonia  till  the  solution 
becomes  a  pasty  mass.  Add  nitric  acid  till  the  iron  is  redis- 
solved  and  the  solution  an  amber  tint. 

Heat  to  70°  C.  and  add  60  cc.  of  the  motybdate  solution. 
Cork  and  shake  thoroughly  for  five  minutes.  Let  stand  at  a 
temperature  of  40°  to  50°  C.  for  an  hour.  Filter  through  a  12. 5 -cm. 
filter.  Wash  thoroughly  with  a  2  per  cent,  nitric  acid  solution. 
Dissolve  the  yellow  precipitate  on  the  filter  in  strong  ammonia 


52  C.  B.  Murray. 

and  let  the  solution  run  through  into  a  5-oz.  beaker  containing 
about  i  gram  citric  acid  dissolved  in  10  cc.  strong  hydrochloric 
acid.  After  all  the  precipitate  has  been  dissolved  and  run 
through  the  filter,  stir  the  solution  in  the  beaker  and  add  10  cc. 
magnesia  mixture  and  fill  up  the  beaker  with  strong  ammonia. 
Stir  a  little  and  set  in  cold  water  till  the  solution  is  cold.  Then 
stir  vigorously  until  the  precipitate  comes  down.  Let  stand  over 
night.  Filter  through  a  9-cm.  filter.  Wash  thoroughly  with 
dilute  ammonia  (i  :  3).  Ignite,  first  at  a  low  temperature,  then 
at  a  higher.  Weigh  as  Mg2P2O7.  Dissolve  the  weighed  pre- 
cipitate in  dilute  nitric  acid  (sp.  gr.  1.20),  heating  crucible  till 
all  is  in  solution.  Filter,  ignite,  and  weigh  the  residue,  which 
is  mainly  silica.  Subtract  this  weight  from  the  first  and  the  dif- 
ference is  pure  Mg2P.jO7. 

SOLUTIONS  USED  IN  PHOSPHORUS  DETERMINATIONS. 

Molybdic  Acid  Solution. — 100  grams  of  molybdic  acid  are  dis- 
solved in  400  cc.  of  ammonia  (sp.  gr.  0.96).  This  is  poured 
into  i  liter  of  nitric  acid  (sp.  gr.  1.20),  thoroughly  stirred,  and 
i  cc.  of  a  solution  of  sodium  phosphate,  containing  5  grams  to 
the  liter,  added.  The  mixture  is  well  shaken  and  allowed  to  stand 
twelve  hours.  The  solution  should  be  perfectly  colorless. 

Magnesia  Mixture. — no  grams  magnesium  chloride  and  280 
grams  ammonium  chloride  are  dissolved  in  1,300  cc.  of  water  and 
700  cc.  ammonia  (sp.  gr.  0.96).  The  solution  should  stand  at 
least  a  week  before  using. 

DETERMINATION  OF  MANGANESE  IN  ORES. 

Dissolve  i  gram  of  the  ore  dried  at  100°  C.  in  25  cc.  strong  hy- 
drochloric acid.  When  all  is  in  solution,  dilute  with  an  equal 
bulk  of  water  and  filter.  Wash  twice  with  hot  water.  Ignite 
the  residue  till  the  filter-paper  is  destroyed.  Cool,  add  to  the 
crucible  two  or  three  drops  of  sulphuric  acid  and  a  little  hydro- 
fluoric acid,  and  evaporate  to  dryness  to  expel  silica.  Fuse  the 
residue  with  about  3  grams  sodium  carbonate.  Dissolve  fusion 
in  the  original  filtrate  from  first  solution,  and  evaporate  this  to 
dryness  in  the  sand-bath.  Take  up  in  150  cc.  strong  nitric  acid. 
Boil  for  about  twenty  minutes,  and  then  add,  a  little  at  a  time,  5 


Edgar  Thomson  Steel   Works  and  Furnaces.  53 

to  8  grams  potassium  chlorate.  When  enough  has  been  added 
to  oxidize  all  the  manganese,  the  solution  will  give  a  little  puff 
and  the  green  fumes  will  disappear.  Now  add  about  i  gram 
more  potassium  chlorate  and  boil  the  solution  for  two  minutes. 
Cool  and  filter  through  a  prepared  asbestos  filter  or  "plug." 
Wash  beaker  and  plug  twice  with  strong  nitric  acid.  The  filtrate 
should  then  be  boiled  and  more  potassium  chlorate  added  to  ascer- 
tain if  all  the  manganese  has  been  precipitated.  The  manganese 
dioxide  on  the  plug,  together  with  the  asbestos,  is  now  returned 
into  the  same  beaker  in  which  the  precipitation  was  made,  dis- 
solved in  25  cc.  hydrochloric  acid  and  boiled  a  few  minutes. 
The  asbestos  is  filtered  off  and  a  few  drops  of  sulphuric  acid  are 
added  to  precipitate  any  barium  which  is  generally  found  in 
manganese  ores.  L,et  stand  about  two  hours.  Now  add  ammo- 
nia till  a  faint  precipitate  appears,  then  25  cc.  of  ammonium 
acetate  solution.  Boil  for  one  minute,  remove  from  the  heat, 
and,  as  soon  as  settled,  filter.  Wash  three  times  with  hot  water. 
Dissolve  precipitate  on  filter  in  hydrochloric  acid  ( i  :  i )  and  let 
run  into  beaker  in  which  first  basic  acetate  separation  was  made. 
Make  a  second  basic  acetate  separation  just  as  the  first.  Com- 
bine the  filtrates  and  dilute  to  about  400  cc.  Add  40  cc.  am- 
monium phosphate  solution  and  then  acidulate  with  hydrochloric 
acid.  Boil  and  add  ammonia,  drop  by  drop  with  constant  stir- 
ring, until  all  the  manganese  is  precipitated  and  the  precipitate 
is  in  the  well-known  crystalline  form.  L,et  the  solution  cool,  fil- 
ter with  suction,  wash  three  times  with  hot  water,  ignite,  and 
weigh  as  MnQP2O7. 

SOLUTIONS   EMPLOYED. 

Ammonium  Acetate  Solution. — Dissolve  450  grams  of  the  salt 
in  8  liters  of  water. 

Ammonium  Phosphate  Solution. — Dissolve  560  grams  of  the 
salt  in  2.5  liters  of  water. 

DETERMINATION    OF    MANGANESE     IN    MANGANIFEROUS     IRON 

ORES. 

Dissolve  i  gram  of  iron  ore  in  50  cc.  hydrochloric  acid. 
Evaporate  to  dryness  on  the  steam-bath.  Take  up  in  20  cc.  nitric 
acid,  and  evaporate  to  about  10  cc.  Wash  into  a  5Oo-cc.  flask, 
dilute  to  about  200  cc.,  and  add  a  solution  of  zinc  oxide  in  water 


54  C.  B.  Murray. 

till  all  the  iron  is  precipitated.  Dilute  to  500  cc.,  make  acid, 
shake  well,  let  settle,  and  decant  off  250  cc.  into  a  flask.  Boil 
for  about  five  minutes.  Titrate  with  a  standard  solution  of  potas- 
sium permanganate. 

DETERMINATION  OF  SILICON  IN  PIG  IRON. 

Dissolve  i  gram  of  iron  in  20  cc.  strong  hydrochloric  acid  in  a 
platinum  dish.  Evaporate  to  dryness  over  a  bare  flame.  Heat 
for  one  minute  after  it  is  dry.  Remove  flame,  add  10  cc.  hydro- 
chloric acid  and  about  25  cc.  water.  Boil,  filter,  ignite,  and 
weigh  as  SiO2. 

DETERMINATION  OF  SULPHUR  IN  PIG  IRON. 

Dissolve  5  grams  in  icocc.  hydrochloric  acid  ( i :  i )  in  a  5<x>-cc. 
flask.  Pass  the  gas  evolved  through  two  |J-tubes  containing 
each  25  cc.  potassium  hydroxide  solution.  After  the  evolution 
of  gas  has  ceased,  heat  the  flask  to  boiling  and  boil  till  inlet-tube 
to  first  y-tube  is  hot.  Remove  the  tube  and  draw  off  the  potas- 
sium hydroxide  solution  from  the  (J-tubesb)7  means  of  a  stop-cock 
at  bottom  into  a  large  porcelain  dish.  Dilute  to  500  cc.  Titrate 
with  a  standard  solution  of  iodine. 

SOLUTIONS  EMPLOYED. 

The  potassium  hydroxide  -solution  contains  i  pound  caustic 
potash  in  17,000  cc.  of  water.  The  starch  solution  is  prepared 
by  dissolving  4  grams  starch  in  a  liter  of  boiling  water  and  de- 
canting the  clear  liquid  for  use. 

The  iodine  solution  is  standardized  by  using  a  standard  steel 
and  also  a  "  shot"  sample.  The  factor  varies  considerably  be- 
tween the  two.  For  pig-iron  drillings  and  steel,  the  steel  factor 
is  used.  For  "  shot"  samples  the  shot  factor. 

DETERMINATION  OF  PHOSPHORUS  IN  PIG  IRON. 

Dissol  ve  i.  63  grams  in  25  cc.  nitric  acid  (sp.gr.  1.20)  ina4j-inch 
dish.  Evaporate  to  dryness  over  a  lamp  and  bake  for  one-half 
hour.  Take  up  in  20  cc.  hydrochloric  acid  and  evaporate  till 
the  volume  of  the  solution  is  about  4  cc.  Add  about  5  cc.  nitric 
acid  and  heat  till  red  fumes  cease  to  come  off.  Dilute  twice 
with  water  and  filter  into  an8-oz  Erlenmeyer  flask.  Add  ammo- 


Edgar  Thomson  Steel   Works  and  Furnaces.  55 

nia  till  a  paste  is  formed,  then  nitric  acid  till  the  solution  shows  an 
amber  color.  Heat  to  40°  C.  and  add  50  cc.  inolybdate  solution. 
Shake  for  five  minutes  and  let  stand  one-half  hour.  Filter  and 
wash  five  times  with  2  per  cent,  nitric  acid  and  twice  with  strong 
alcohol.  The  filters  are  then  placed  in  a  water-bath  and 
heated  one  hour,  removed,  and  weighed  in  a  "  clip."  Of  course 
the  filter-papers  should  have  been  heated  one  hour  and  weighed 
previously.  Since  we  started  with  1.63  grams,  calling  the  per- 
centage of  phosphorus  in  yellow  precipitate  1.63,  every  milli- 
gram equals  o.ooi  per  cent,  phosphorus. 

The  solutions  are  the  same  as  used  in  an  ore  analysis. 

DETERMINATION  OF  MANGANESE  IN  PIG  IRON. 

i  gram  of  iron  is  dissolved  in  25  cc.  nitric  acid  (sp.  gr.  1.20), 
evaporated  to  about  10  cc.;  then  proceed  as  in  case  of  manga- 
nese in  manganiferous  iron  ores. 

DETERMINATION  OF  CARBON  IN  STEEL. 

In  case  of  steels  of  over  0.50  per  cent,  carbon  take  i  gram  ; 
for  steels  under  0.50  take  2  grams.  Dissolve  in  100  cc.  in  first 
case,  or  150  cc.  in  second,  of  the  double  chloride  of  copper  and 
potassium  solution.  The  process  may  be  hastened  by  stirring  and 
heating  to  about  80°  C.  After  all  is  in  solution  filter  into  a 
platinum  boat,  wash  four  or  five  times  with  dilute  hydrochloric 
acid  ( i  :  i )  and  with  hot  water.  For  the  combustion  a  platinum 
tube  is  used  containing  six  inches  of  copper  oxide  held  in  place 
by  platinum  gauze. 

The  oxygen  used  in  the  combustion  is  purified  by  passage, 
first  through  a  bottle  of  potash  solution,  and  second  through  a 
jar  of  solid  potash,  upon  which  a  layer,  one  inch  deep,  of  calcium 
chloride  rests.  A  ten-burner  Bunsen  furnace  is  used. 

Two  burners  are  lighted  under  the  copper  oxide  in  the  plati- 
num tube.  When  this  point  is  red  hot  all  the  burners  are 
lighted  and  oxygen  passed  through  for  half  an  hour.  The  car- 
bon dioxide  is  caught  in  a  solution  of  barium  hydroxide  in  a 
Meyer  tube  containing  six  bulbs.  For  carbon  under  i  per  cent., 
25  cc.  of  a  saturated  solution  of  barium  hydroxide  is  sufficient. 
This  amount  will  about  fill  four  of  the  bulbs  in  the  tube.  At  the 


56  Edgar  Thomson  Steel   Works  and  Furnaces. 

end  of  half  an  hour  the  oxygen  is  shut  off  and  air  passed 
through  the  same  train  for  fifteen  minutes.  The  Meyer  bulb  is 
then  detached  and  the  solution  filtered  through  a  9-cm.  filter 
using  suction.  By  means  of  a  rubber  tube  connected  with  the 
train  a  jet  of  air  is  forced  into  the  funnel  during  filtering,  keeping 
an  atmosphere  free  from  carbon  dioxide  surrounding  the  filter- 
paper.  The  tube  is  easily  washed  clean.  The  filter-paper  with 
precipitated  barium  carbonate  is  put  into  a  platinum  crucible 
and  the  crucible  subjected  to  gentle  heat  until  the  filter-paper  is 
burnt,  then  placed  in  a  muffle  furnace  and  heated  till  white.  It 
is  weighed  as  BaCO3  and  carbon  calculated. 

SOLUTIONS  EMPLOYED. 

Double  Chloride  of  Copper  and  Potassium. — 2,250  grams  of  the 
double  salt  are  dissolved  in  6.5  liters  of  water  and  0.5  liter  hy- 
drochloric acid  added. 

The  barium  hydroxide  solution  contains  20  grams  of  the  com- 
mercial baryta  dissolved  in  i  liter  of  water. 

DETERMINATION  OF  SULPHUR  IN  STEEL. 

5  grams  of  steel  are  dissolved  in  100  cc.  hydrochloric  acid 
(i  :  i).  From  this  point  on,  the  method  employed  is  the  same 
as  in  the  case  of  pig  iron. 

DETERMINATION  OF  PHOSPHORUS  IN  STEEL- 

Dissolve  1.63  grams  of  steel  in  25  cc.  nitric  acid  (sp.  gr.  1.20), 
and  proceed  in  the  same  manner  as  in  the  case  of  pig-iron,  ex- 
cept that  it  is  not  necessary  to  filter  off  graphite. 

DETERMINATION  OF  MANGANESE  IN  STEEL. 

Dissolve  i  gram  in  25  cc.  nitric  acid  (sp.  gr.  1.20)  and  pro- 
ceed as  in  the  case  of  pig  iron. 

DETERMINATION  OF  NICKEL  IN  STEEL. 

Use  the  method  given  by  Blair,  in  ( '  Chemical  Analysis  of 
Iron,"  Third  Edition,  p.  184. 


IX.  METHODS  USED  AT  THE  LABORATORY  OF  THE 
CLINTON  IRON  AND  STEEL  CO.,  PITTSBURG,  PA. 


BY  A.  B.  HARRISON. 

DETERMINATION   OF   SILICA   IN    IRON   ORES. 

The  ore  is  treated  according  to  the  directions  given  in  Blair's 
"  Analysis  of  Iron,"  Third  Edition,  p.  239. 

DETERMINATION   OF    IRON    IN   ORES. 

The  sample  is  dissolved  in  concentrated  hydrochloric  acid, 
the  insoluble  residue  fused  with  sodium  carbonate,  and  the 
fusion  dissolved  in  dilute  hydrochloric  acid.  Ths  solution  of 
ferric  chloride  obtained  is  reduced  with  stannous  chloride,  the 
excess  of  the  latter  being  oxidized  with  mercuric  chloride.  The 
reduced  iron  solution  is  titrated  with  potassium  bichromate. 

DETERMINATION    OF    PHOSPHORUS   IN   ORES. 

The  sample  is  dissolved  in  hydrochloric  acid,  the  insoluble 
residue  fused  with  sodium  carbonate,  and  the  fusion  dissolved 
in  dilute  sulphuric  acid.  The  filtrate  from  the  insoluble  resi- 
due and  the  filtrate  from  the  solution  of  its  fusion  are  combined, 
precipitated  with  ammonia  (sp.  gr.  0.96),  and  the  precipitate 
dissolved  in  nitric  acid  (sp.  gr.  1.13).  The  determination  is 
then  proceeded  with  as  in  the  case  of  steel. 

DETERMINATION   OF   MANGANESE    IN   ORES. 

See  the  method  described  for  determination  of  manganese  in 
pig  iron,  p.  58. 

DETERMINATION    OF   SILICON    IN    PIG    IRON. 

Drown's  method  somewhat  modified  is  used.  Dissolve  0.4667 
gram  of  drillings  in  "  silicon  mixture"  in  a  covered  porcelain 
dish,  and  evaporate  the  solution  to  dryness  without  removing 
the  cover.  When  the  dish  is  sufficiently  cool  wash  off  the  watch- 
glass  into  the  dish,  and  rinse  down  the  sides  of  the  dish  with  hot 
dilute  hydrochloric  acid  ( i  :  i )  until  the  volume  of  the  liquid  is 


58  A.  B.  Harrison. 

50  cc.  Boil  until  all  iron  salts  are  dissolved,  filter  with  the  aid 
of  suction,  and  wash  alternately  with  hot  water  and  dilute  hydro- 
chloric acid  until  all  iron  is  washed  out.  Burn  and  weigh. 
Ashless  filters  being  used,  no  calculation  beyond  "  pointing  off" 
will  be  necessary,  as  can  readily  be  seen. 

The  silicon  mixture  is  made  as  follows :  Mix  1,500  cc.  of  water, 
500  cc.  of  nitric  acid  of  1.40  sp.  gr.,  and  150  cc.  of  sulphuric  acid 
of  1.84  sp.  gr. 

DETERMINATION   OF   SULPHUR    IN    PIG    IRON. 

The  determination  of  sulphur  is  carried  out  according  to  the 
11  iodine  method"  as  given  in  Blair's  "Analysis of  Iron,"  Third 
Edition,  pp.  68-71.  In  this  form  the  method  is  the  iodine 
method  as  modified  by  Mr.  E.  T.  Wood.. 

DETERMINATION   OF   PHOSPHORUS    IN    PIG    IRON. 

For  this  purpose  I  use  Emmerton's  method  as  described  by 
Dr.  Dudley. 

DETERMINATION   OF   MANGANESE   IN    PIG   IRON. 

Manganese  is  determined  according  to  a  modification  of  Vol- 
hard's  method.  One  gram  of  drillings  is  dissolved  in  100  cc.  of 
silicon  mixture  in  a  porcelain  evaporating  dish.  After  solution 
5  cc.  of  concentrated  hydrochloric  acid  are  added,  and  the  con- 
tents of  the  dish  evaporated  to  dry  ness.  The  cover  of  the  dish 
is  washed  off  with  hot  water  and  the  residue  taken  up  with  100 
cc.  of  water.  Boil  till  all  iron  salts  are  dissolved.  Transfer  the 
solution  without  filtering  to  a  liter  flask,  and  dilute  with  water  to 
300  cc.  Bring  the  contents  of  the  flask  to  boiling,  and  add  pure 
zinc  oxide  suspended  in  water  till  all  iron  is  precipitated  and 
zinc  oxide  is  present  in  slight  excess.  Titrate  the  contents  of 
the  flask  while  boiling  hot  and  without  filtering  with  potassium 
permanganate  solution. 

DETERMINATION    OF     SILICON,     SULPHUR,    PHOSPHORUS,     MAN- 
GANESE,   AND   NICKEL   IN   STEEL. 

Silicon  is  determined  as  described  in  Blair's  "  Analysis  of 
Iron,"  Third  Edition,  p.  72. 


Clinton  Iron  and  Steel  Company.  59 

Sulphur  is  estimated  by  the  method  given  for  pig  iron.  The 
aqua  regia  method  is  used  for  checking. 

Phosphorus  is  determined  as  in  pig  iron.  Results  are  checked 
by  the  "  magnesia  method." 

For  nickel  determinations  the  method  of  A.  T.  Eastwick  is 
used.  See  Proceedings  of  the  Engineers'  Society  of  Western 
Pennsylvania,  9,  170. 

Manganese  is  determined  by  the  method  described  for  pig  iron. 


X.  METHODS  USED  AT  THE  LABORATORY  OF  THE 
ISABELLA  FURNACE  CO.,  ETNA,  PA. 


BY  F.  G.  BRINKER. 

DETERMINATION    OF   SILICA    IN    IRON    ORES. 

Dissolve  i  gram  finely  powdered  ore  in  hydrochloric  acid, 
dilute,  filter,  wash,  and  fuse  residue  with  a  mixture  of  sodium 
and  potassium  carbonates.  The  fusion  is  dissolved  in  a  beaker 
in  hydrochloric  acid.  Evaporate  to  dry  ness  and  bake.  Dis- 
solve in  hydrochloric  acid,  dilute  the  solution,  filter,  wash  the 
residue  with  hot  water,  dilute  hydrochloric  acid,  and  again  with 
hot  water.  Burn  and  weigh. 

DETERMINATION    OF    IRON    IN    IRON    ORES. 

Dissolve  i  gram  of  ore,  finely  pulverized,  in  a  flask  in  40  cc. 
hydrochloric  acid,  at  a  gentle  heat.  Add  i  gram  of  potassium 
chlorate.  Place  a  funnel  in  the  neck  of  the  flask  and  boil  gently 
till  chlorine  is  expelled.  Dilute  to  50  cc.,  heat  nearly  to  boil- 
ing, and  deoxidize  with  a  solution  of  stannous  chloride  measured 
by  means  of  a  burette.  Cool,  and  titrate  back  the  excess  of 
stannous  chloride  with  a  solution  of  iodine. 

If  greater  accuracy  be  required  filter  and  fuse  the  insoluble 
residue,  dissolve  in  acid,  and  add  to  the  main  solution  before 
deoxidizing. 

In  preparing  the  standard  iron  solution,  fine  iron  wire  is  used 
and  treated  as  above  described.  The  first  factor  is  found  by 
standardizing  the  stannous  chloride  and  iodine  solutions.  Take 
2  cc.  of  stannous  chloride  solution,  dilute,  add  a  little  starch 
solution,  and  titrate  with  iodine  solution.  Divide  the  number 
of  cubic  centimeters  of  iodine  into  the  number  of  cubic  centi- 
meters of  stannous  chloride.  Multiply  the  number  of  cubic  cen- 
timeters of  iodine  used  to  titrate  back  the  excess  of  stannous 
chloride  used  by  this  factor,  and  subtract  from  the  total  volume 
of  stannous  chloride  used  for  the  reduction.  The  second  factor 
is  found  by  dividing  the  number  of  cubic  centimeters  of  stannous 


Isabella  Furnace  Company.  61 

chloride,  used  for  the  standard  after  the  excess  has  been  sub- 
tracted, into  the  weight  of  pure  iron  in  the  iron  taken. 

Multiply  the  number  of  cubic  centimeters  of  stannous  chloride 
solution  by  this  and  by  100.  This  gives  the  per  cent,  of  iron  in 
the  sample. 

SOLUTIONS   EMPLOYED. 

Stannous  Chloride  Solution. — Dissolve  60  grams  of  crystals  in 
125  cc.  hydrochloric  acid  and  125  cc.  water.  To  this  solution 
there  are  added  650  cc.  hydrochloric  acid  and  1,650  cc.  water. 

Iodine  Solution. — This  contains  8  grams  iodine  dissolved  in 
potassium  iodide  solution  and  diluted  to  i  liter. 

I  use  also  the  permanganate  method  as  described  by  Blair, 
deoxidizing  by  zinc.  When  titanium  is  present,  I  use  acid 
ammonium  sulphate. 

DETERMINATION  OF  MANGANESE  IN  IRON   ORES   AND  PIG  IRON. 

I  use  Williams'  method  and  also  Volhard's  as  described  in 
Blair's  "Chemical  Analysis  of  Iron,  "Third  Edition,  pp.  112-117. 

DETERMINATION   OF    PHOSPHORUS   IN    IRON    ORE. 

I  use  the  molybdate-magnesia  method  as  described  by  Blair 
in  "Chemical  Analysis  of  Iron,"  Third  Edition, p.  89. 

DETERMINATION   OF   SILICON    IN    PIG   IRON 

Dissolve  0.9333  gram  of  drillings  in  a  casserole  in  hydrochloric 
acid,  and  evaporate  to  dry  ness.  Cool  and  take  up  with  hydro- 
chloric acid,  heating  the  mixture  to  boiling.  Dilute,  filter, 
wash  with  dilute  hydrochloric  acid,  and  finally  with  hot  water. 
Ignite  cautiously  until  the  filter  has  been  burned  off.  The  igni- 
tion is  then  continued  for  fifteen  minutes  at  the  highest  heat  of 
a  gas  blast-lamp.  Cool  and  weigh.  The  weight  of  the  silica 
found  divided  by  2  and  multiplied  by  100  gives  the  percent- 
age of  silicon. 

DETERMINATION    OF    PHOSPHORUS   IN    PIG   IRON. 

Weigh  1.63  grams  of  well-mixed  borings  into  a  5oo-cc.  beaker 
and  add  cautiously  35  cc.  nitric  acid  of  1.20  sp.  gr.  Boil  down 
to  dryness,  and  bake  on  a  hot  plate  at  200°  C.,  for  thirty  minutes. 
Redissolve  in  hydrochloric  acid.  Add  35  cc.  of  concentrated 
nitric  acid  and  evaporate  until  the  volume  of  the  liquid  is  reduced 


62  Isabella  Furnace  Company. 

to  about  15  cc.  Remove  from  hot  plate,  dilute  with  hot  water, 
filter,  and  to  the  filtrate  add  ammonia  until  a  precipitate  forms 
which  does  not  disappear  en  stirring.  The  neutralized  solution 
is  treated  with  3  cc.  of  concentrated  nitric  acid,  which  should 
suffice  to  redissolve  the  precipitate  and  give  a  clear,  amber- 
colored  liquid,  not  red  in  tint.  The  solution  is  then  heated  to 
about  70°  C.,  the  molybdate  solution  added,  and  the  mixture 
shaken  for  five  minutes.  Let  the  precipitate  settle,  collect  it  on 
a  weighed  filter,  and  wash  with  water  containing  2  per  cent,  of 
nitric  acid.  Dry  in  the  air-bath  at  120°  C.  for  thirty  minutes 
after  all  visible  moisture  has  disappeared,  and  weigh. 


XI.  METHODS  USED  AT  THE  LABORATORY  OF  THE 

SHENANGO  VALLEY  STEEL  CO., 

NEW  CASTLE,  PA. 


BY  WARREN  R.  CLIFTON. 

DETERMINATION   OF    SIIyICA   AND    IRON    IN    ORES. 

Weigh  i  grain  of  the  sample  into  a  No.  2  beaker,  add  25  cc. 
of  strong  hydrochloric  acid,  cover  with  a  watch-glass,  and  digest 
at  a  temperature  just  short  of  boiling  until  the  ore  is  decomposed; 
dilute  with  25  cc.  of  water  and  filter  into  a  No.  4  beaker.  The 
residue  is  then  burned  and  fused  with  sodium  carbonate,  the 
fusion  dissolved  in  the  filtrate  from  the  residue,  and  the  whole 
allowed  to  go  to  hard  dryness.  Redissolve  the  mass  in  about 
15  cc.  of  strong  hydrochloric  acid,  dilute,  filter  into  a  3OO-cc. 
flask,  and  wash  the  residue  three  or  four  times  with  hot  water; 
ignite  and  weigh  as  SiO2.  In  the  filtrate  the  iron  is  deoxidized 
by  granulated  zinc  and  determined  by  titration  with  a  standard 
bichromate  solution  ;  the  addition  of  the  standard  is  continued 
until  a  drop  of  the  iron  solution  added  to  a  drop  of  potassium 
ferricyanide  solution  no  longer  produces  a  blue  coloration  on 
standing  one-half  minute.  The  number  of  cubic  centimeters 
of  bichromate  solution  used  multiplied  by  one  hundred  times 
the  value  of  i  cc.  in  iron,  gives  the  percentage  of  iron. 

Potassium  Bichromate  Solution. — Dissolve  17.570  grams  of  the 
fused  salt  in  water,  dilute  to  2  liters,  and  standardize  with  iron 
wire. 

DETERMINATION    OF    PHOSPHORUS    IN    ORES. 

Digest  5  grams  of  the  samples  dried  at  100°  C.,  in  a  No.  2 
beaker,  covered  by  a  watch-glass  in  50  cc.  of  strong  hydrochloric 
acid.  When  the  ore  appears  to  be  perfectly  decomposed,  dilute, 
and  filter  into  a  No.  5  beaker.  The  residue  is  burned  and 
fused  with  sodium  carbonate,  the  fusion  dissolved  in  hot  water, 
the  solution  acidified  with  strong  hydrochloric  acid,  added  to  the 
original  filtrate,  and  the  combined  solutions  allowed  to  go  to 
hard  dryness  on  the  hot  plate.  The  mass  is  then  moistened  with 


64  Warren  R.   Clifton, 

a  little  hydrochloric  acid,  diluted  with  a  sufficient  amount  of 
water  to  dissolve  the  sodium  salt,  and  filtered  into  a  4co-cc. 
Erlenmeyer  flask.  The  process  is  then  carried  on  as  in  the  case 
of  steel. 

DETERMINATION  OF    MANGANESE    IN    IRON    ORES. 

2  grams  of  ore  are  dissolved  and  further  treated  in  the  same 
manner  as  for  phosphorus  and  the  solution  filtered  into  a  5oo-cc. 
flask.  The  solution  is  neutralized  with  ammonia  until  a  slight 
permanent  precipitate  forms.  Redissolve  this  with  a  few  drops 
•  of  hydrochloric  acid,  and  add  ammonium  carbonate,  drop  by 
drop,  until  a  faint  precipitate  is  formed.  Add  about  4  grams  of 
sodium  acetate,  boil  one  minute,  and  allow  the  precipitate  to 
settle.  Filter  into  a  5co-cc.  flask,  and  wash  two  or  three  times  with 
hot  water.  The  precipitate  is  washed  back  into  the  same  flask 
in  which  the  precipitation  was  made,  and  dissolved  in  the  least 
possible  quantity  of  hydrochloric  acid.  The  precipitation  is 
repeated  exactly  as  before.  Unite  the  filtrates  and  proceed  as 
in  the  case  of  steel. 

DETERMINATION    OF   SILICON    IN    PIG    IRON. 

Twice  the  factor- weight— 0.9340  gram  of  drillings — is  weighed 
off  into  a  No.  5  beaker.  Add  50  cc.  of  water,  and  then  pour 
into  the  mixture  20  cc.  of  sulphuric  acid  (sp.  gr.  1.85),  direct- 
ing the  acid  to  the  center  of  the  beaker.  Evaporate  until  copious 
fumes  of  sulphur  trioxide  are  given  off.  Cool  the  beaker  over  a 
cold  blast  jet.  Add  100  cc.  of  water  and  4  or  5  cc.  of  hydro- 
chloric acid.  Boil  until  all  sulphate  of  iron  has  dissolved,  filter 
hot,  wash  at  first  with  dilute  hydrochloric  acid  ( i  :  i ) ,  and  then 
with  hot  water  ;  ignite  and  weigh.  One-half  the  weight  in 
decimilligrams  is  the  per  cent,  of  silicon  in  hundredths. 

DETERMINATION    OF   SULPHUR    IN    IRON    AND    STEEL. 

Dissolve  5  grams  of  drillings  in  a  No.  5  beaker,  covered  by  a 
watch-glass,  in  50  cc.  of  strong  nitric  acid.  When  the  violent 
action  has  ceased,  add  15  cc.  of  strong  hydrochloric  acid,  and, 
when  solution  is  complete,  about  one-half  gram  of  sodium  car- 
bonate. Evaporate  the  solution  to  hard  dryness.  Remove 
the  beaker  from  the  heat  ;  when  cold  add  40  cc.  of  strong  hydro- 


Shenango    Valley  Steel  Company.  65 

chloric  acid,  and  heat  gently  at  first,  unt^  the  oxide  of  iron  is 
dissolved  ;  evaporate  again  to  syrup,  and,  if  any  ferric  chloride 
separates,  add  a  few  drops  of  strong  hydrochloric  acid  ;  dilute, 
and  filter,  washing  with  the  least  possible  amount  of  dilute  hydro- 
to  remove  the  last  trace  of  iron.  Heat  the  filtrate, 
have  a  volume  of  about  400  cc.,  to  boiling,  add 
5  cc.  of  a  saturated  solution  of  barium  chloride,  and  allow  to 
stand  at  about  40°  C.  over  night.  Filter  through  a  Q-cm. 
Munktell's  No.  i  filter  ;  wash  with  a  little  dilute  hydrochloric 
acid  (i  :  i),  and  finally  with  hot  water  ;  dry,  ignite,  and  weigh 
as  BaSO4. 


DETERMINATION  OF   SULPHUR    IN    PIG    IRON    AND 

Evolution  Method.  —  Place  3  grams  of  drillings  in  a  dry  5OO-cc. 
flask,  provided  with  a  doubly  perforated  rubber  stopper  ;  the 
stopper  carries  a  one-bulb  thistle-tube,  and  a  small  piece  of  glass 
tubing  bent  at  right  angles  ;  the  latter  is  connected  by  a  short 
piece  of  rubber  tubing  to  a  glass  tube  running  to  the  bottom  of 
an  intervening  bottle  ;  the  exit-tube  of  the  bottle  is  connected 
by  rubber  tubing  to  a  de^ery-tube,  also  bent  at  right  angles, 
reaching  to  the  bottom  or  a  one-inch  by  eight-inch  specimen- 
tube.  Connected  by  a  rubber  stopper  and  delivery-  tube  with  this 
is  a  second  specimen-tube.  The  whole  apparatus  is  suitably 
supported.  Dilute  15  cc.  of  an  ammoniacal  cadmium  chloride 
solution  to  100  cc.  with  cold  water,  and  pour  one-half  into  each 
of  the  specimen-tubes.  About  100  cc.  of  boiling  water  is  added 
to  the  500-cc.  flask,  and  the  flask  connected  with  the  apparatus 
above  described.  Introduce,  through  the  thistle-  tube,  50  cc.  of 
strong  hydrochloric  acid.  When  the  sample  has  dissolved,  boil 
the  solution  until  the  steam  reaches  the  first  specimen-tube,  then 
disconne^at  the  latter,  turn  out  the  light,  and  allow  the  flask 
to  draw  Wck  the  acid  and  water  which  has  distilled  into  the 
intervening  bottle.  Transfer  the  contents  of  the  specimen-  tubes 
torn  40<Ap.  Erlenmeyer  flask,  rinsing  the  tubes  with  a  little 
hydrochloric  acid  and  water.  Now  add  a  few  cc.  of  starch  solu- 
tion, acidulate  with  strong  hydrochloric  acid,  and  immediately 
run  in  the  iodine  solution  from  a  burette,  agitating  the  con- 
tents of  the  flask  at  the  same  time,  until  the  proper  blujlcolor  is 


66  Warren  R.   Clifton. 

obtained.  The  volpnevin  cubic  centimeters  of  iodine  solution 
used  multiplied  by  the  value  of  i  cc.,  is  the  percentage  of  sulphur 
in  the  sample. 

Cadmium  Chloride  Solution. — Dissoifc  120  grams  of  cadmium 
chloride  in  1,500  cc.  of  water,  and  adcffloo  cc.  of  strong 

Iodine  Solution. — Weigh  out  into  a  half-liter  flask  3  of 

iodine,  and  20  grams  of  potassium  ™dide.     Add  al 
of  water.     Allow  to   stand   over   nig^t  and   dilute 
The  solution  is  standardized  with  an  iron  of  known  sulphur-con- 
tent.    The  known  percentage  of  sulphur  divided  by  the  num- 
ber of  cubic  centimeters  of  solution  required  is  the  strength  of 
the  iodine  solution. 

DETERMINATION     OF     PHOSPHORUS    IN    PIG     IRON   AND    STEEL. 

3  grams  of  drillings  are  dissolved  in  a  No.  5  beaker  in  40  cc. 
of  nitric  acid  (sp.  gr.  1.20)  and  the  solution  evaporated  to  hard 
dry  ness.  Allow  the  beaker  to  cool,  dissolve  the  precipitate  in 
30  cc.  of  strong  hydrochloric  acid^dilute  with  cold  water,  filter 
into  a  4OO-cc.  Brlenmeyer  flask,  and  wash  the  filter  with  cold 
water.  Add  10  cc.  of  strong  ammonia  and  agitate  the  mixture 
until  the  precipitate  formed  is  all  dissolved.  The  solution  is 
heated  or  cooled  to  60°  C.,  and  50  cc.  of  molybdate  solution  are 
added  by  aid  of  a  pipette  ;  the  flask  is  shaken  for  two  or  three 
minutes  and  then  allowed  to  stand  till  the  precipitate  has  settled. 
Filter,  collect  the  precipitate  on  a  y-crn.  S.  &  S.  No.  589  filter, 
and  wash  with  dilute  molybdate  solution  (water  containing  5 
per  cent,  of  its  volume  of  the  above).  Pour  3  or  4  cc.  ammonia 
on  the  precipitate,  stir  it  up  with  a  fine  jet  of  water,  and  allow 
the  solution  to  run  into  the  flask  in  which  the  precipitation  was 
made.  Add  drop  by  drop  enough  strong  hydrochloric  acid  to 
cause  the  separation  of  the  yellow  precipitate,  and  thejjammon|a 
until  it  redissolves.  Pour  the  solution  back  througir  thevfilter, 
allowing  it  to  run  into  a  i2o-cc.  Erlenmeyer  flask,  and  wash 
two  or  three  times  with  cold  water.  To  the  cold  ^«tio«idd 
very  slowly  10  cc.  of  magnesia  mixture,  agitating  'constantly, 
and,  after  the  precipitant  is  all  in,  5  cc.  of  strong  ammonia. 
Shake  vigorously.  Stand  the  flask  in  cold  water  for  about  one 
hour  ;  Ifcter  on  a  y-cm.  S.  &S.  No.  589  paper,  and  wash  with  5  per 


Shenango    Valley  Steel  Company.  67 

cent,  ammonia.     Ignite  over  the  blast-lamp  at  a  low  heat,  and 
weigh  as  Mg2P207. 

Molybdate  Solution. — Dissolve  100  grams  of  molybdic  acid  in 
of    strong   ammonia.      Pour    1,250  cc.  of  nitric    acid 
>o),  into  a  2.5-liter  bottle,  and  place  the  bottle  in  a 
water.     Now  add,  in  small  portions,  the  molybdic 
ammonia,  taking  about  thirty  minutes  in  the  operation, 
h'xture  is  kept  in  a  warm  place  for  forty-eight  hours  and 
is  then  ready  for  use. 

Magnesia  Mixture. — Dissolve  280  grams  of  ammonium  chloride 
together  with  no  grams  of  magnesium  chloride  in  1,300  cc.  of 
water,  and  add  700  cc.  of  strong  ammonia.  Allow  the  solution 
to  stand  four  or  five  days  before  using. 

DETERMINATION     OF   MANGANESE     IN    STEEL     AND     PIG   IRON. 

Dissolve  3  grams  of  drillings  in  a  No.  5  beaker  in  50  cc.  of 
nitric  acid  (sp.  gr.  1.20),  evaporate  until  the  solution  is  almost 
of  a  sirupy  consistence,  add  100  cc.  of  strong  nitric  acid,  heat 
the  solution  to  boiling,  and  while  boiling  add  5  grams  of  potas- 
sium chlorate  in  small  portions.  Continue  the  boiling  for  ten 
minfctes.  Cool  the  solution  rapidly  by  standing  the  beaker  in  a 
panfcf  cold  water  ;  filter  by  aid  of  a  pump  through  purified 
asbestos  supported  by  a  small  piece  of  pumice  stone  in  the  stem 
of  the  filtering  tube  ;  wash  two  or  three  times  with  strong  nitric 
acid.  Transfer  the  precipitate,  with  the  asbestos  filter,  to  the 
beaker  in  which  the  precipitation  was  made.  The  filtering  tube 
is  washed  off  with  water  and  a  little  hydrochloric  acid  ;  add 
about  5  cc.  of  hydrochloric  acid,  and  agitate  the  contents  of  the 
beaker  until  the  asbestos  is  all  suspended.  Heat  the  mixture 
till  the  precipitate  is  dissolved ;  filter  from  the  asbestos  into  a 
No.  2  bearer,  and  wash  with  hot  water.  To  the  filtrate  add 
enough  ammonium  acetate  to  precipitate  the  last  traces  of  iron, 
boil,p£nd  ^er  into  a  4oo-cc.  Erlenmeyer  flask. 

Tj  the  ^Prate  add  an  excess  of  strong  ammonia,  and  then, 
with  a  vigorous  shake,  a  few  cubic  centimeters  of  bromine. 
Heat  gradually  to  boiling,  allow  the  precipitate  to  settle,  filter, 
and  wash  with  cold  water.  The  washing  of  the  precipitate 
is  easily  accomplished  by  means  of  cold  water,  there  bjpng  no 


68  Warren  R.   Clifton. 

fixed  alkali  presenfc     Ignite  over  a  blast-lamp  at  |Jiow  heat 
and  weigh  as  MnsO4. 

In  the  case  of  pig  iron,  dissolve  in  50  cc.  of  dilute  h] 
acid.      Dilute  and  filter  into  a  No.  5  beaker,  evap< 
nearly  to  a  sirup,  being  careful  not  to  heat  too  stron 
solve  in  50  cc.  strong  nitric  acid,  and  evaporate  to 
sion  of  hydrochloric  acid.      Add   100  cc.  of  strong  niti 
heat  to  boiling,  add  5  grams  of  potassium  chlorate,  and 
as  described  for  steel. 

Determination  of  Manganese  by  the  Color  Method. — In  case  of 
steel  o.i  gram  of  each  sample  and  of  the  standard,  is  measured 
off  into  i -inch  by  8-inch  test-tubes.  Pour  into  each  test-tube* 
15  cc.  of  nitric  acid  (sp.  gr.  1.20).  When  the  violent  action  has 
ceased  boil  over  an  Argand  burner  till  nitrous  fumes  are  driven 
off.  While  boiling,  add  about  five-tenths  of  a  gram  of  lead  per- 
oxide, and  boil  each  sample  and  the  standard  exactly  one 
minute.  The  tubes  thus  filled  are  immediately  placed  in  cold 
water  and  set  aside  in  a  dark  place.  When  cool,  and  the  excess 
of  peroxide  has  settled  out  leaving  the  supernatant  liquid  per- 
fectly clear,  the  standard  solution  is  decanted  into  one  of  the 
comparing  tubes.  The  solution  is  then  diluted  with  water  to  as 
many  cubic  centimeters  as  the  standard  contains  hundredAis  of 
i  per  cent,  of  manganese,  and  mixed  thoroughly  witifc  the 
water.  The  test  sample  is  decanted  in  the  same  manner$and 
diluted  with  cold  water  until  it  has  the  same  shade  as  the  stand- 
ard solution.  The  reading  in  cubic  centimeters  represents  the 
percentage  of  manganese  in  hundredths. 

In  the  case  of  pig  iron  it  is  preferable  to  dissolve  one  gram 
each  of  the  sample  and  of  a  pig  iron  standard  in  a  No.  2  beaker 
in  75  cc,  of  nitric  acid  of  1.13  sp.  gr.  Dilute  to  100  cc.  with  cold 
water  and  filter  a  portion  through  a  dry  filter.  Draw  out  10  cc. 
of  this  solution  with  a  pipette  and  let  it  run  into  a  test-tube. 
Add  5  cc.  of  nitric  acid  of  1.20  sp.  gr.,  and  proc^d  as  %i  the 
case  of  steel. 

DETERMINATION   OF    MANGANESE    IN    IRON   ORES. 

2  grams  of  ore  are  dissolved  as  in  the  case  of  a  determination  of 
phosjfcorus,  and  filtered  into  a  5oo-cc.  flask.  The  solution  is 


Shenango    Valley  Steel  Company.  69 

neutralized  by  ammonia,  and  a  slight  permanent  precipitate  pro- 
duced. Redissolve  this  precipitate  in  a  few  drops  of  hydro- 
chloric acid,  and  add  ammonium  carbonate,  drop  by  drop,  until 
a  precipitate  begins  to  form.  Then  add  4  grams  sodium  acetate, 
and  jMJkfor  one  minute.  Allow  the  precipitate  to  subside.  Fil- 
ter ifS(  r*5oo-cc.  flask  and  wash  two  or  three  times  with  hot 
water.  The  precipitate  is  washed  back  into  the  flask  in  which 
it  ^Hl  formed,  by  breaking  the  filter  with  a  glass  rod,  and  dis- 
solved in  the  least  possible  quantity  of  hydrochloric  acid.  Re- 
peat the  precipitation  exactly  as  before,  unite  the  filtrates,  and 
proceed  as  in  the  case  of  steel. 

DETERMINATION   OF    NICKEL   IN   STEEL. 

Dissolve  one  gram  of  drillings  in  a  No.  4  beaker  in  25  cc.  of 
nitric  acid  (sp.gr.  1.20),  and  evaporate  to  hard  dry  ness.  Redis- 
solve in  15  cc.  of  strong  hydrochloric  acid  and  separate  the  iron 
exactly  as  directed  in  the  determination  of  manganese  in  ores^. 
Unite  the  filtrates  and  boil  down  until  their  volume  is  reduced 
to  about  300  cc.  Acidulate  with  a  few  drops  of  acetic  acid, 
heat  to  boiling,  and  pass  hydrogen  sulphide  till  the  solution  smells 
strongly  of  the  gas.  Boil  a  few  minutes  until  the  precipitate  has 
a  flocculent  appearance.  Filter  and  wash  with  hot  water,  ignite 
the  filter  and  precipitate,  and  transfer  them  to  a  No.  2  beaker. 
Dissolve  in  3  or  4  cc.  of  strong  hydrochloric  acid  with  a  few 
drops  of  strong  nitric  acid,  evaporate  to  dryness,  redissolve  in 
a  few  drops  of  strong  hydrochloric  acid,  dilute  to  about  100  cc., 
heat  to  boiling  and  pass  hydrogen  sulphide  through  the  solution, 
let  the  precipitate  subside,  filter  if  necessary,  wash  with  hot 
water  and,  if  desired,  burn  and  weigh  as  Cu2S.  To  the  filtrate  add 
an  excess  of  ammonia,  pass  hydrogen  sulphide,  allow  the  pre- 
cipitate to  settle,  filter,  wash,  ignite  in  a  porcelain  crucible,  and 
weigh  as  NiO. 


XII.  METHODS  USED  AT  THE  LABORATORY  OF 

THE  PENNSYLVANIA  RAILROAD  COMPANY, 

ALTOONA,  PA. 


BY  C.  B.  DUDLEY  AND  F.  N.  PHASE.1 
"  Method  of  Determining  Carbon  in  Iron  and  Steel."     Bf  C. 

B.  Dudley  and  F.  N.   Pease.     American  Engineer  and  Railroad 

Journal,  July,  1893,  p.  347. 

"  Method  of  Determining  Carbon  in  Iron  and  Steel."     By  C. 

B.  Dudley  and  F.  N.  Pease.     American  Engineer  and  Railroad 
Journal,  August,  1893,  p.  391. 

4 '  The  Need  of  Standard  Methods  for  the  Analysis  of  Iron  and 
Steel,  with  Some  Proposed  Standard  Methods."  By  C.  B. 
Dudley  and  F.  N.  Pease.  Journal  of  the  American  Chemical 
Society,  September,  1893,  p.  501. 

"  Method  of  Determining  Sulphur  in  Steel."  By  C.  B. 
Dudley  and  F.  N.  Pease.  American  Engineer  and  Railroad 
Journal,  September,  1893,  p.  443. 

"  Standard  Methods  for  the  Analysis  of  Iron  and  Steel."     By 

C.  B.  Dudley.     Proceedings  Chemical  Section,  Engineers'  Society, 
W.  A.j.October,  1893. 

"  Method  of  Determining  Sulphur  in  Pig  and  Wrought  Iron." 
By  C.  B.  Dudley  and  F.  N.  Pease.  American  Engineer  and  Rail- 
road Journal,  December,  1893,  p.  579. 

1  In  publishing  in  the  Proceedings  of  the  Chemical  Section  of  the  Engineers'  Society 
of  W.  Pa.,  the  methods  of  chemical  analysis  in  use  at  the  different  iron  and  steel  works 
laboratories,  it  has  been  the  practice  heretofore,  to  print  the  methods  in  detail  as  de- 
scribed by  the  senders.  In  the  case  of  the  methods  of  Dr.  C.  B.  Dudley  and  Mr.  F.  N. 
Pease,  of  the  Pennsylvania  Railroad  Laboratory  at  Altoona,  an  exception  has  been 
made.  Dr.  Dudley,  in  charge  of  the  Altoona  Laboratory,  has  kindly  placed  at  the  dis- 
posal of  the  Committee,  the  details  of  the  admirable  methods  so  fully  and  clearly  de- 
scribed in  the  publications  of  the  Pennsylvania  Railroad  Laboratory.  These  methods 
have,  however,  been  repeatedly  reproduced  in  technical  journals,  and  in  the  transactions 
of  various  scientific  societies,  and  they  are  already  so  well  known  to  chemists  that  a  de- 
tailed account  of  them  seems  hardly  necessary.  In  place  of  complete  details,  therefore, 
a  list  of  references  to  the  papers  of  Dr.  Dudley  and  Mr.  Pease  is  here  given. 

Some  of  the  papers  do  not  deal  with  single  methods  of  determination  of  the  constitu- 
ents of  iron  and  steel,  but  are  of  such  general  interest  that  it  seems  eminently  proper 
that  they  should  be  included  among  the  papers  upon  methods. 


Pennsylvania  Railroad  Company.  71 

"  Method  of  Determining  Manganese  in  Steel."  By  C.  B. 
Dudley  and  F.  N.  Pease.  American  Engineer  and  Railroad 
Journal,  April,  1894.,  p.  176. 

"  An  Attempt  to  Find  the  Amount  of  Phosphorus  in  Three 
Samples  of  Steel."  By  C.  B.  Dudley  and  F.  N.  Pease. 
Journal  of  the  American  Chemical  Society ,  April,  1894.,  p.  217. 

"  On  Some  Points  in  the  Determination  of  Phosphorus  in 
Steel  by  the  Volumetric  Method."  By  C.  B.  Dudley  and  F.  N. 
Pease.  Journal  of  the  American  Chemical  Society,  April,  1894., 
p.  224. 

"Method  of  Determining  Silicon  in  Steel."  By  C.  B.  Dudley 
and  F.  N.  Pease.  American  Engineer  and  Railroad  Journal, 
July,  1894,  p.  321. 

"  Method  of  Determining  Phosphorus  in  Steels."  By  C.  B. 
Dudley  and  F.  N.  Pease.  Separate  paper  published  by  the 
Pennsylvania  Railroad  Company. 

The  methods  above  mentioned  for  the  determination  of  carbon 
and  of  sulphur  in  steel  are  also  published  and  distributed  by  the 
Pennsylvania  Railroad  Company. 


XIII.    METHODS    USED    AT    THE  LABORATORY    OF 
McINTOSH,  HEMPHILL&  CO.,  PITTSBURG,  PA. 

BY  J.  P.  M'KELVEY. 


DETERMINATION   OF   SILICA    IN    IRON   ORES. 

Fuse  with  sodium  carbonate,  dissolve  in  hydrochloric  acid 
and  evaporate  to  dry  ness,  moisten  the  residue  with  hydrochlo- 
ric acid,  take  up  with  water,  filter,  wash,  ignite,  and  weigh. 

DETERMINATION  OP  IRON  IN  IRON  ORES. 

The  filtrate  from  the  silica  serves  for  the  iron  determination. 
Reduce  in  a  6oo-cc.  Erlenmeyer  flask  with  tested  zinc,  and 
titrate  with  bichromate  as  usual,  using  potassium  ferricyanide 
as  an  indicator. 

DETERMINATION   OF    MANGANESE    IN    IRON   ORES. 

Dissolve  i  gram  of  ore  in  hydrochloric  acid  and  evaporate  to 
dryness.  Redissolve  in  50  cc.  of  nitric  acid  (sp.  gr.  1.42),  and 
proceed  as  in  Ford's  method. 

DETERMINATION   OF   PHOSPHORUS   IN    IRON   ORES. 

Dissolve  5  to  10  grams  of  ore  in  hydrochloric  acid  and  evap- 
orate to  dryness.  Take  up  in  a  small  amount  of  hydrochloric 
acid,  dilute,  filter,  and  proceed  as  in  the  acetate  method,  sepa- 
rating arsenic  by  hydrogen  sulphide. 

DETERMINATION    OF   SILICON    IN    PIG    IRON. 

Dissolve  i  gram  of  drillings  in  30  cc.  of  dilute  hydrochloric 
acid  and  evaporate  to  dryness.  Moisten  the  residue  with  hydro- 
chloric acid,  dilute,  filter,  wash,  ignite,  and  weigh. 

DETERMINATION    OF    SULPHUR    IN    PIG   IRON. 

As  given  in  Blair's  " Analysis  of  Iron,"  Third  Edition,  p.  65, 
under  the  heading  "  By  Oxidation  and  Solution." 

DETERMINATION   OF    PHOSPHORUS   IN   PIG   IRON. 

The  acetate  method  is  used. 


Mclntosh,  Hemphill  &  Co.  73 

DETERMINATION   OF    MANGANESE    IN    PIG    IRON. 

This  determination  is  made  by  the  color  method  as  given  in 
Blair's  "Analysis  of  Iron,"  Third  Edition,  p.  126,  with  the  ex- 
ception that,  after  solution  of  the  drillings  and  before  diluting  to 
100  cc.,  the  solution  is  filtered. 

DETERMINATION  OF  SULPHUR,    PHOSPHORUS,  MANGANESE,  AND 
NICKEL   IN   STEEL. 

Sulphur  and  phosphorus  are  determined  according  to  the 
methods  already  detailed  for  pig  iron  ;  manganese  by  the  color- 
imetric  method  described  in  Blair's  "  Analysis  of  Iron,"  Third 
Edition,  p.  126  ;  for  nickel  determination  see  Blair's  "Analysis 
of  Iron,"  Third  Edition,  p.  184. 


XIV.  METHODS  USED  AT  THE  LABORATORY  OF  THE 
W.  DEWEES  WOOD  COMPANY,  McKEESPORT,  PA. 


BY  THEO.  TONNELE  AND  R.  B.  CARNAHAN,  JR. 


DETERMINATION    OF   SILICA   IN    IRON   ORES. 

The  sample,  which  has  passed  through  a  loo-mesh  sieve,  is 
dried  thoroughly  at  100°  C.  just  previous  to  analysis. 

Fuse  i  gram  of  the  ore  with  5  grams  sodium  carbonate  and  0.25 
gram  potassium  nitrate  in  a  platinum  crucible.  Acidify  with 
hydrochloric  acid  and  evaporate  todryness.  Redissolve  in  suffi- 
cient water  and  hydrochloric  acid,  filter,  wash  with  dilute  hydro- 
chloric acid  (sp.  gr.  i.io)  and  hot  water,  ignite,  and  weigh. 
Treat  the  ignited  residue  in  the  usual  way  with  hydrofluoric 
acid  and  a  few  drops  of  sulphuric  acid  ;  the  loss  in  weight  repre- 
sents the  quantity  of  silica  in  the  ore. 

DETERMINATION   OF   IRON   IN   ORES. 

Dissolve  0.75  gram  in  concentrated  hydrochloric  acid,  heating 
on  the  steam-bath  over  night.  Deoxidize  the  ferric  iron  of  the 
solution  with  stannous  chloride,  adding  the  latter  gradually. 
When  the  solution  is  entirely  colorless,  cool  somewhat,  and  then 
add  10  cc.  of  mercuric  chloride  solution.  Titrate  in  the  regular 
way  with  standard  potassium  bichromate,  using  a  very  dilute 
solution  of  potassium  ferricyanide  to  determine  the  end-reaction. 

Solutions. — The  mercuric  chloride  is  a  saturated  aqueous  solu- 
tion. The  stannous  chloride  solution  contains  150  grams  of  the 
salt  dissolved  in  i  liter  of  hydrochloric  acid  (i.io  sp.  gr.).  To 
prepare  the  standard  bichromate,  dissolve  7  grams  of  the  salt  in 
i  liter  of  water,  and  dilute  so  that  i  cc.  is  equivalent  to  0.0075 
gram  of  iron.  The  solution  is  standardized  from  a  steel  of  known 
composition. 

DETERMINATION   OF   PHOSPHORUS   IN   ORES. 

From  3  to  5  grams  of  ore  (according  to  the  percentage  of  phos- 
phorus) are  dissolved  in  strong  hydrochloric  acid,  and  the  solu- 


IV.  Dewees   Wood  Company.  75 

tion  evaporated  to  dryness  ;  the  residue  is  redissolved  in  a  few 
cc.  of  strong  hydrochloric  acid  and  water  ;  and  the  silicious 
matter  remaining  filtered  off  and  ignited.  The  latter  is  fused 
with  a  little  sodium  carbonate,  the  fusion  dissolved  in  nitric  acid 
and  water,  and  the  nitric  solution  added  to  the  original  filtrate, 
which  is  again  evaporated  to  dryness.  After  dissolving  in  a 
little  hydrochloric  acid  and  water,  the  silica  is  removed  by  filtra- 
tion. The  filtrate  is  made  slightly  alkaline  with  ammonia,  and 
then  slightly  acidified  with  nitric  acid.  The  solution,  which 
measures  about  100  cc.,  is  heated  to  80°  C.;  50  cc.  of  molybdate 
solution  are  added,  and,  after  standing  for  about  one  minute,  the 
mixture  is  agitated  for  five  minutes  by  passing  a  stream  of  air  or 
natural  gas  through  it.  The  yellow  precipitate  is  filtered 
by  the  aid  of  suction  and  washed  with  pure  water.  It  is 
then  titrated  with  standard  alkali,  the  solution  being  standard- 
ized by  steels  and  pig  irons  in  which  the  phosphorus  has  already 
been  determined  by  the  molybdate-magnesia  method,  according 
to  Blair's  "Analysis  of  Iron,"  Third  Edition,  p.  89. 

Solutions. — The  molybdate  solution  is  made  by  dissolving  i 
pound  of  molybdic  acid  in  1,000  cc.  of  strong  ammonia,  and  1,000 
cc.  of  water,  and  pouring  this  solution  into  6J  liters  of  nitric  acid 
(sp.gr.  1.20). 

DETERMINATION   OF    MANGANESE    IN   ORES 

From  3  to  5  grams  of  ore  are  dissolved  in  strong  hydrochloric 
acid,  and  the  solution  evaporated  to  dryness.  The  dry  mass  is 
redissolved  in  hydrochloric  acid  and  water,  and  the  insoluble 
residue  filtered  off  and  ignited.  The  residue  is  fused  with 
sodium  carbonate  and  the  fusion  dissolved  in  hydrochloric  acid 
and  water.  The  solution,  after  separating  the  silica,  is  added  to 
the  main  solution  ;  potassium  chlorate  is  then  added,  care  being 
taken  to  expel  the  chlorine  generated  in  excess.  The  iron  is 
precipitated  as  basic  acetate,  the  precipitate  being  redissolved 
and  reprecipitated  twice.  For  each  gram  of  ore  2  grams  of 
ammonium  acetate  are  used.  The  combined  filtrates  are  then 
concentrated  and  the  manganese  precipitated  by  bromine  as  di- 
oxide. The  precipitate  is  filtered  off  and  dissolved  in  hydro- 
chloric acid,  the  solution  neutralized  with  ammonia,  and  the  man- 


76  Theo.    Tonnele  and  R.  B.   Catnahan,Jr. 

ganese  again  precipitated  as  ammonium  manganese  phosphate, 
according  to  Blair.  Ignite  and  weigh  as  manganese  pyrophos- 
phate,  Mn2P2OT.  When  the  percentage  is  less  than  0.5,  the 
manganese  dioxide  is  converted  for  weighing  into  protosesqui- 
oxide. 

DETERMINATION    OP    SILICON    IN    PIG    IRON. 

Dissolve  i  gram  of  borings  in  35  cc.  of  "  silicon  mixture," 
and  evaporate  until  the  formation  of  fumes  of  sulphur  tri- 
oxide  begins.  When  sufficiently  cool,  dissolve  in  a  little  water 
and  about  TOCC.  of  strong  hydrochloric  acid.  Filter,  using  suc- 
tion, wash  with  hot  water  and  dilute  hydrochloric  acid 
(i.io  sp.  gr.),  ignite,  and  weigh  as  silica. 

Solutions. — The  "  silicon  mixture"  is  made  by  adding  100  cc. 
of  strong  sulphuric  acid  to  900  cc.  of  nitric  acid  (1.20  sp.  gr.). 

DETERMINATION    OF   SULPHUR    IN    PIG   IRON. 

Weigh  into  a  5oo-cc.  flask,  5  grams  of  drillings,  add  50 
cc.  of  water,  and,  after  connecting  the  flask  with  the  absorption 
apparatus,  add  50  cc.  of  strong  hydrochloric  acid.  Without 
delay  light  a  small  flame  under  the  flask,  and  dissolve  as  rapidly 
as  desired.  The  evolved  gas  bubbles  through  50  cc.  of  ammo- 
niacal  cadmium  chloride  solution  contained  in  a  y-inch  foot  test- 
tube.  When  the  drillings  have  dissolved,  boil  the  solution  to 
expel  the  last  traces  of  hydrogen  sulphide  from  the  flask. 
Rinse  out  the  contents  of  the  test-tube  into  a  shallow  porcelain 
dish,  made  slightly  acid  with  hydrochloric  acid,  add  starch  solu- 
tion, and  titrate  to  a  decided  blue  color  with  a  standard  iodine 
solution. 

Solutions. — Ammoniacal  cadmium  chloride  solution  is  made 
by  dissolving  30  grams  of  cadmium  chloride  in  5  liters  of  water 
and  i  liter  of  strong  ammonia.  The  iodine  solution  is  prepared 
by  dissolving  8.5  grams  of  iodine  and  about  25  grams  of  potas- 
sium iodide  in  a  small  quantity  of  water,  and  diluting  to  2  liters. 
This  solution  is  then  exactly  standardized  by  a  standard  steel 
(rather  high  in  sulphur)  in  which  the  percentage  of  sulphur  has 
been  exactly  determined  by  the  aqua  regia  method,  as  described 
by  Blair  in  his  /'  Chemical  Analysis  of  Iron,"  Third  Edition, 


W.  Dewees    Wood  Company.  77 

p.  65.    Except  only  in  a  very  few  cases,  all  pig  irons  are  tested  for 
sulphur  by  the  evolution  method. 

DETERMINATION    OF   PHOSPHORUS   IN    PIG   IRON. 

Dissolve  3  grams  of  the  sample  in  50  cc.  of  nitric  acid 
(1.20  sp.  gr.),  evaporate  to  dryness,  and  heat  the  residue  over 
a  bare  flame  for  five  minutes.  Cool,  dissolve  in  a  few  cc.  of 
strong  hydrochloric  acid,  and  evaporate  until  the  solution 
measures  about  10  cc.  Then  add  about  20  cc.  of  strong  nitric 
acid,  and  boil  for  about  four  minutes.  Dilute  with  water  and 
filter.  The  solution  should  have  a  volume  of  about  75  cc. 
Complete  the  determination  as  in  the  case  of  ores. 

For  the  sake  of  rapidity  we  use  the  following  method  for 
several  grades  of  Bessemer  pig  iron :  Dissolve  3  grams  of  the 
metal  in  100  cc.  of  nitric  acid  (sp.  gr.  1.13).  When  the  borings 
have  completely  dissolved  add  a  saturated  solution  of  potas- 
sium permanganate  till  a  decided  precipitate  remains.  Boil 
three  minutes  and  then  add  10  cc.  of  strong  hydrochloric  acid. 
Filter  off  the  carbonaceous  residue  and  proceed  further  as  de- 
scribed for  ores. 

DETERMINATION   OF   MANGANESE    IN    PIG   IRON. 

Dissolve  3  to  5  grams  of  the  sample  in  50  cc.  of  nitric  acid 
(sp.  gr.  i. 20),  evaporate  to  dryness,  and  ignite  for  five  minutes. 
Cool,  redissolve  in  a  few  cc.  of  hydrochloric  acid,  evaporate  the 
excess  of  acid,  and  filter.  Make  the  basic  acetate  separation, 
etc.,  as  described  under  iron  ores. 

The  color  method  is  also  used  largely  for  pig  irons ;  viz.,  dis- 
solve 0.5  gram  of  pig  iron  in  15  cc.  of  nitric  acid  (sp.  gr.  1.20) 
in  an  8-inch  test-tube,  filter,  and  dilute  the  filtrate  to  50  cc. 
Draw  off  10  cc.  with  a  pipette  and  place  the  solution  in  an 
8-inch  test-tube.  Add  3  cc.  of  nitric  acid  (sp.  gr.  1.20). 
Heat  to  boiling,  add  about  0.2  gram  of  lead  peroxide, 
and  boil  the  mixture  for  two  minutes.  Add  about  15 
cc.  of  cold  water,  and  allow  the  tube  to  stand  in  cold  water  till 
the  lead  peroxide  settles  completely.  Compare  the  color  of  the 
sample  for  analysis  with  that  of  a  standard  pig  iron  treated  simi- 
larly. Standards  are  always  made  by  the  basic  acetate  method, 
the  manganese  being  weighed  as  pyrophosphate. 


78  Theo.    Tonnele  and  R.  B.   Carnahan,  Jr. 

DETERMINATION    OF  SULPHUR    IN   STEEL. 

See  Pig  Iron. 

DETERMINATION   OF   PHOSPHORUS   IN   STEEL. 

See  Pig  Iron.  The  permanganate  oxidation  method  is 
generally  used  ;  filtering  off  the  silica  becomes  unnecessary 
in  this  case. 

DETERMINATION   OF   CARBON    IN    STEEL. 

Dissolve  3  grams  of  steel  in  200  cc.  of  a  saturated  solution  of 
cupric  potassium  chloride,  containing  10  cc.  of  strong  hydro- 
chloric acid,  at  60°  C.,  with  constant  stirring. 

Filter  off  the  carbonaceous  residue  on  an  asbestos  plug,  and 
wash  with  dilute  hydrochloric  acid  and  hot  water. 

Transfer  the  residue  to  a  5oo-cc.  flask  and  burn  with  a  mixture 
of  chromic  and  sulphuric  acids,  absorbing,  for  weighing,  the  car- 
bon dioxide  evolved. 

The  combustion  train  is  as  follows  : 

1.  A  500-cc.  flask. 

2.  An  empty  tube. 

3.  A  tube  containing  : 

0.2  gram  pyrogallic  acid, 
5      grams  potassium  oxalate, 
3      grams  sodium  chloride, 
0.2  gram  sulphuric  acid,  and 

water  sufficient  to  make  the  volume  20  cc. 

4.  A  tube  containing  silver  sulphate  and  strong  sulphuric  acid. 

5.  A  tube  containing  sulphuric  acid. 

6.  An  empty  tube. 

7.  Geissler  potash  bulbs  containing  caustic  potash   (sp.  gr. 
1.27);  and  a  guard  l|-tube  containing  strong  sulphuric  acid. 

After  the  combustion,  pure  air  is  aspirated  through  the  ap- 
paratus for  twenty  minutes. 

Blanks  are  made,  and  the  apparatus  frequently  checked  by 
steels  of  known  carbon  content.  The  various  minute  details  are 
carried  out  about  as  given  in  Blair's  work  above  quoted. 


W.  Dewees   Wood  Company.  79 

DETERMINATION   OF   MANGANESE   IN   STEEL. 

See  Pig  Iron.  The  silica  filtration  is  not  generally  necessary, 
however. 

DETERMINATION   OF    NICKEL   IN   STEEL. 

Make  the  basic  acetate  separation,  using  i  gram  of  steel,  and 
to  the  filtrate  add  10  grams  of  ammonium  acetate  and  6  drops  of 
acetic  acid.  Precipitate  with  hydrogen  sulphide,  filter,  burn, 
and  weigh  as  NiO  (and  CuO,  should  copper  be  present). 

Dissolve  the  ignited  precipitate  in  hydrochloric  acid,  and  a 
few  drops  of  nitric  acid,  dilute  with  water,  and  precipitate  any 
copper  in  the  solution  with  hydrogen  sulphide. 

Ignite  and  weigh  as  CuO  ;  subtract  the  weight  from  the  first 
weight.  The  difference  represents  the  quantity  of  NiO  derived 
from  the  sample. 


XV.  METHODS  USED  AT  THE  LABORATORY  OF  THE 
OHIO  STEEL  COMPANY,  YOUNGSTOWN,  OHIO. 


BY  J.  C.  BARRETT. 

DETERMINATION   OF   SILICA   IN   ORES. 

Weigh  off  5  grams  ore  which  has  been  dried  at  100°,  dissolve 
in  75  cc.  strong  hydrochloric  acid,  evaporate  to  dry  ness,  add  30 
cc.  strong  hydrochloric  acid,  and  when  dissolved  dilute  and 
filter,  washing  with  dilute  hydrochloric  acid  and  water.  The 
residue  is  then  burned  and  fused.  The  fusion  is  dissolved  in 
water,  made  acid  with  hydrochloric  acid,  and  evaporated  to  dry- 
ness.  Take  up  with  hydrochloric  acid  and  water,  filter,  and 
wash  well  with  water.  Place  in  crucible  wet,  heat  gently  until 
dry  and  the  paper  is  well  charred,  then  heat  in  a  muffle  until  white. 
Weigh  as  soon  as  cold.  Observe  precautions  for  titanic  acid 
and  barium  sulphate. 

DETERMINATION   OF   IRON   IN   ORES. 

The  ore  is  dried  at  100°  for  one  hour  and  cooled  in  a  desic- 
cator. Weigh  quickly  5  grams  of  the  ore,  dissolve  in  a  dish  with 
75  cc.  concentrated  hydrochloric  acid  and  evaporate  to  dry  ness 
on  a  sand-bath.  Redissolve  in  30  cc.  strong  hydrochloric  acid, 
and  when  alt  is  in  solution  evaporate  to  a  very  small  bulk  or 
near  sticking-point.  Dilute  with  hot  water  and  filter,  washing  with 
as  little  dilute  hydrochloric  acid  as  possible.  Wash  well  with  hot 
water.  Burn  silicious  residue  and,  if  colored  at  all  with  iron,  fuse. 
Dissolve  and  make  acid  with  hydrochloric  acid  and  evaporate  to 
dry  ness  to  separate  the  silica.  Take  up  with  as  little  hydro- 
chloric acid  as  possible  and  filter  into  the  main  solution,  which 
should  be  in  a  graduated  5oo-cc.  flask,  calibrated  accurately 
with  a  loo-cc.  pipette.  Keep  at  room  temperature,  fill  with 
water  of  same  temperature  to  mark,  and  mix  well.  Take 
loo  cc.,  with  same  pipette  you  have  checked  flask  with,  and 
put  into  a  clean  flask  of  5oo-cc.  capacity,  fitted  with  a  rubber 
stopper  having  a  Bunsen  valve.  Add  100  cc.  sulphuric  acid 


Ohio  Steel  Company.  81 

(i  :  4),  and  then  15  grams  of  zinc.  Keep  cool  for  a  time,  then 
add  10  grams  more  of  zinc  if  necessary.  When  all  action  is 
over,  raise  to  a  good  heat,  but  not  to  boiling.  Cool,  pour  into  a 
No.  5  beaker  into  which  50  cc.  of  sulphuric  acid  (1:4)  has 
been  poured  ;  wash  out  flask  well,  decanting  from  residue  caused 
by  the  zinc,  filling  the  beaker  to  a  little  more  than  half  full;  and 
titrate  with  a  standard  solution  of  potassium  permanganate,  ma- 
king allowance  for  a  blank  on  zinc  which  is  carried  along  side  by 
side  with  the  ore,  using  the  same  weight  of  zinc  in  blanks  as  for 
ore.  In  presence  of  titanium  reduce  with  hydrogen  sulphide. 
Remove  the  hydrogen  sulphide  and  titrate. 

DETERMINATION    OF    PHOSPHORUS   IN    ORES. 

Dissolve  5  grams  of  ore  in  75  cc.  of  strong  hydrochloric  acid  and 
treat  in  the  same  way  as  for  iron,  except  that  there  is  added  a 
little  nitric  acid  on  the  first  evaporation.  When  the  second 
evaporation  reaches  the  sticking-point  add  3  or  4  drops  of  hydro- 
chloric acid,  dilute  and  filter  into  a  i6-oz.  flask,  wash,  and  then 
burn  the  residue  and  fuse.  Dissolve  the  fusion  in  water,  make  acid 
with  hydrochloric  acid,  and  evaporate;  take  up  with  as  little 
acid  as  possible,  dilute  with  water,  and  filter  into  the  flask  with 
first  solution.  Add  25  cc.  ammonia,  then  25  cc.  concentrated 
nitric  acid  which  should  just  redissolve  the  precipitate  and  leave 
the  liquid  slightly  acid .  Heat  the  solution  in  the  flask  to  85°  exactly, 
and  add  75  cc.  ammonium  molybdate  solution  and  shake  for 
five  minutes.  When  it  has  stood  for  one-half  hour,  or  until 
settled,  filter  through  a  9-cm.  Munktell  paper,  which  has  been 
dried  for  one  hour  at  110°  and  weighed  between  watch-glasses, 
as  soon  as  taken  from  oven.  In  presence  of  arsenic  or  titanium 
follow  Blair's  acetate  method  after  getting  the  main  filtrate  and 
that  from  the  fused  residue  united,  down  to  the  basic  acetate  pre- 
cipitate carrying  the  phosphorus.  This  is  put  into  a  small 
beaker,  paper  and  all,  and  dissolved  in  a  mixture  of  dilute  nitric 
and  hydrochloric  acids,  at  a  gentle  heat.  Filter  from  paper  and 
evaporate  to  expel  hydrochloric  acid  ;  now  filter  into  a  i6-oz. 
flask  and  precipitate  phosphorus  as  above  with  ammonium  molyb- 
date solution  at  85°.  When  necessary  or  desirable  the  yellow 
precipitate  and  paper  are  put  into  a  small  beaker,  treated  with 


82  /.   C.  Barrett. 

dilute  ammonia,  the  paper  and  silica  separated,  and  phosphorus 
precipitated  with  magnesia  mixture. 

The  yellow  precipitate  is  washed  well  with  2  per  cent,  nitric 
acid  solution,  excess  of  moisture  removed  with  blotting-paper 
and  dried  in  an  oven  at  110°,  taking  from  oven  and  weighing  at 
once  between  the  watch-glasses. 

The  ammonium  molybdate  solution  is  made  by  dissolving  200 
grams  molybdic  acid  in  500  cc.  water  with  500  cc.  ammonia, 
and  adding  2,500  cc.  of  nitric  acid  (sp.  gr.  1.20),  and  keeping  in 
a  warm  place  for  twenty-four  hours. 

DETERMINATION   OF    MANGANESE   IN   ORES. 

Dissolve  5  grams  of  ore  in  75  cc.  concentrated  hydrochloric  acid, 
evaporate  to  dryness,  take  up  with  hydrochloric  acid,  and  when 
in  solution  evaporate  to  a  small  bulk.  Filter  into  a  5Oo-cc.  flask. 
Burn  residue  after  washing,  fuse,  dissolve  fusion  in  water,  make 
acid,  and  evaporate  to  dryness.  Take  up  with  a  small  quantity  of 
hydrochloric  acid,  dilute  with  water,  and  filter  into  main  solution. 
If  little  manganese  is  present,  evaporate  the  whole  in  a  No.  4 
beaker  to  sirupy  consistency  with  concentrated  nitric  acid  twice. 
If  manganese  be  in  large  quantity,  fill  flask  to  mark  and  take  a 
measured  quantity  after  shaking  up  well,  and  evaporate  as 
above.  Then  add  100  cc.  concentrated  nitric  acid,  heat  to  boil- 
ing and  precipitate  manganese  dioxide  with  potassium  chlorate 
and  boil  for  a  few  minutes.  Remove  from  the  lamp  and  cool. 
Filter  through  asbestos  filter  and  wash  once  with  colorless  nitric 
acid.  When  dry,  transfer  asbestos  and  precipitate  to  original 
beaker  and  wash  filtering  tube  with  concentrated  hydrochloric 
acid  and  hot  water,  washing  down  the  sides  of  the  beaker  with 
same,  using  about  18  cc.  hydrochloric  acid.  Heat,  while  shaking, 
over  a  lamp,  until  manganese  dioxide  is  entirely  dissolved.  Filter 
off  asbestos  receiving  the  solution  in  a  i6-oz.  flask.  Wash  well 
and  make  a  basic  acetate  precipitation.  Filter  from  this  precipi- 
tate into  a  No.  6  beaker.  Redissolve  the  precipitate  with  hydro- 
chloric acid  and  repeat  the  basic  acetate,  filtering  into  the  original 
solution.  Make  solution  in  beaker  acid  with  acetic  acid,  heat 
to  boiling,  and  precipitate  manganese  as  phosphate  with 
ammonium  phosphate ;  boil  until  the  precipitate  is  crystalline, 


Ohio  Steel  Company.  83 

stirring  if  necessary  ;  then  add  25  cc.  ammonia,  boil  for  a  few 
minutes,  remove  from  heat,  and,  when  settled,  filter  and  wash 
five  times  with  water.  Absorb  excess  of  water  on  blotter  and 
put  precipitate  in  crucible.  Char  with  lid  on,  then  remove  it 
and  ignite  until  white.  Weigh  as  Mn2P2O7. 
Use  precautions  for  lead  or  barium. 

DETERMINATION   OF   SILICON    IN    PIG   IRON. 

Weigh  off  0.9404  gram  of  iron,  dissolve  in  25  cc.  of  a  mixture 
of  28  parts  of  nitric  acid  (sp.  gr.  1.20)  and  12  parts  of  dilute 
sulphuric  acid  (i  :  i).  As  soon  as  solution  is  complete,  evapo- 
rate over  burner.  Use  a  4^-inch  evaporating  dish.  When  dry, 
raise  the  heat  until  copious  fumes  of  sulphur  trioxide  escape. 
Cool,  add  a  few  cc.  of  dilute  hydrochloric  acid  (3:5)  and  25  cc. 
of  hot  water.  Replace  over  the  lamp  until  solution  is  complete. 
Filter,  wash  paper  once  with  hot  water,  then  once  with  dilute 
hydrochloric  acid,  and  three  or  four  times  again  with  hot  water; 
absorb  excess  of  water  from  paper  and  residue  with  blotting- 
paper.  Place  in  crucible  and  burn  in  a  muffle,  cool,  weigh,  and 
divide  by  2.  Result  —  silicon. 

DETERMINATION   OF   SULPHUR   IN    PIG   IRON    AND   STEEL. 

Evolution  Method. — Weigh  5  grams,  place  in  a  i6-oz.  flask, 
closed  with  a  funnel-tube  and  exit-tube  for  gas  which  is  con- 
nected with  a  tube  extending  to  the  bottom  of  a  i-inch  by  10- 
inch  test-tube.  This  test-tube  is  filled  two- thirds  full  of  a  cad- 
mium chloride  solution.  In  the  bottom  of  the  tube  is  placed 
about  i  inch  of  ammoniacal  solution  of  cadmium  chloride. 
(This  is  made  by  dissolving  100  grams  in  500  cc.  water  and 
adding  500  cc.  ammonia  ;  filter  into  a  2- gallon  bottle  and  add 
enough  water  to  make  3  liters  and  enough  ammonia  to  make  5 
liters.)  After  adding  i  inch  of  this  cadmium  chloride  solution, 
fill  tube  two-thirds  with  water.  To  drillings  in  flask  add  So  cc.  di- 
lute hydrochloric  acid  (3  :  5),  place  over  an  Argand  burner  and 
heat  until  quite  warm  ;  lower  the  heat  until  solution  is  complete, 
then  increase  the  heat  until  steam  drives  all  gas  from  flask.  Discon- 
nect flask  and  pour  the  solution  from  the  hot  tube  with  the  yellow 
sulphide  into  a  No.  4  beaker.  Wash  out  the  tube  with  water  and 


84  /.   C.  Barrett. 

enough  dilute  hydrochloric  acid  to  make  solution  in  beaker  acid 
and  dissolve  the  sulphide.  This  is  titrated  immediately  with  a 
standard  solution  of  iodine  which  has  been  standardized  with  a 
sulphur  standard  so  as  to  read  percentage.  Each  o.  i  cc.  =  o.ooi 
per  cent,  sulphur.  While  titrating  be  sure  that  all  sulphide  is 
dissolved.  The  beaker  should  be  two-thirds  full. 

Aqua  Regia  Method. — Weigh  5  grams,  place  in  a  No.  4 
beaker,  add  a  mixture  of  5  cc.  strong  hydrochloric  acid  and  40 
cc.  strong  nitric  acid  to  drillings  at  once.  Heat  until 
solution  is  complete,  add  40  cc.  strong  hydrochloric  acid,  trans- 
fer to  a  No.  2  beaker  or  a  4^-inch  dish,  and  evaporate  to  hard  dry- 
ness.  Do  not  ignite.  Cool,  add  30  cc.  concentrated  hydro- 
chloric acid,  dissolve  and  evaporate  to  formation  of  a  crust,  add 
10  or  12  drops  of  hydrochloric  acid,  dilute,  and  filter  into  a  No.  2 
beaker.  Wash  well  and  fill  beaker  three-fourths  full,  heat  to 
boiling  and  precipitate  with  3  cc.  barium  chloride  solution  (25 
grams  to  500  cc.  water).  Allow  to  stand  over  night  on  a  warm 
plate  or  sand-bath,  then  evaporate  to  formation  of  scum,  add  a  few 
drops  of  hydrochloric  acid  and  dilute  with  water  to  about  one- 
half  beaker  full,  evaporate  again  to  scum,  add  a  few  drops  of 
hydrochloric  acid  to  redissolve  and  dilute  to  two-thirds  full  with 
cold  water  and  allow  to  stand  at  room  temperature  over  night. 
Filter  through  a  double  filter  No.  589,  7  cm.,  wash  well  with  hy- 
drochloric acid  and  water,  and  burn  in  an  open  crucible.  Purify 
this  precipitate  if  necessary. 

DETERMINATION     OF     PHOSPHORUS     IN    PIG     IRON    AND    STEEL. 

Dissolve  5  grams  in  a  4^-inch  dish,  using  60  cc.  of  nitric  acid 
(sp.  gr.  i. 20)  for  steel,  and  70  cc.  for  pig  iron.  When  the  solu- 
tion is  complete,  which  will  take  a  few  minutes  for  steel  and 
about  twenty  minutes  to  a  half  hour  for  pig-iron,  evaporate  over 
Argand  burner  with  watch-glass  cover,  having  flame  as  high  as 
possible  without  smoking.  When  nearly  dry  lower  the  heat  so 
that  any  iron  that  may  have  splashed  up  on  the  watch-glass 
may  be  redissolved  and  carried  down  into  the  dish.  As  soon  as 
dry,  remove  the  watch-glass  and  heat  over  the  lamp  until  all  acid 
fumes  are  gone.  Cool  and  add  to  pig  iron  35  cc.  strong  hydro- 
chloric acid,  and  to  steel  30  cc. ;  replace  the  watch-glass  and 


Ohio  Steel  Company.  85 

place  over  a  low  heat  until  solution  is  complete  ;  then  raise  the 
heat  and  evaporate  as  rapidly  as  possible  withe  over  on,  until  the 
solution  is  of  a  very  dark  color,  and  about  to  adhere  to  the  dish. 
Remove  from  lamp,  add  5  cc.  strong  nitric  acid,  shake  about 
until  well  mixed  and  any  that  adheres  to  the  sides  may  be  dis- 
solved ;  dilute  with  hot  water  to  about  100  cc.,  washing  off  the 
watch-glass.  Filter  into  a  i6-oz.  flask,  washing  paper  and  resi- 
due with  two  per  cent,  nitric  acid  and  hot  water.  Add  25  cc. 
strong  ammonia,  shake  up,  and  then  redissolve  with  25  cc.  of 
strong  nitric  acid,  leaving  solution  but  slightly  acid.  Heat  to 
85°  and  add  75  cc.  ammonium  molybdate  solution.  Shake  for 
five  minutes.  When  well  settled,  filter  through  a  9-crn.  Munk- 
tell  filter,  which  has  been  dried  at  110°  for  one  hour,  and  weigh 
between  watch-glasses.  Wash  well  with  2  per  cent,  solution  of 
nitric  acid  and  dry  at  1 10°  for  one  hour.  Weigh  between  watch- 
glasses.  If  arsenic  or  titanium  be  present,  follow  Blair's  acetate 
method  after  filtering  from  residue  down  to  the  basic  acetate 
precipitate  carrying  phosphorus.  This  precipitate  is  dissolved 
in  a  dilute  solution  of  nitric  and  hydrochloric  acids  in  a  small 
beaker  and  warmed.  Filter  from  paper,  remove  hydrochloric 
acid  by  evaporation,  filter  into  a  i6-oz.  flask,  and  precipitate  with 
ammonium  molybdate  solution. 

If  desirable  and  thought  necessary  dissolve  yellow  precipitate 
in  dilute  ammonia,  by  putting  paper  and  all  in  beaker.  Re- 
move paper  and  silica  and  make  magnesium  precipitate. 

MANGANESE    IN    IRON    AND    STEEL. 

Color  Method. — Weigh  2  grams  iron  or  steel,  place  in  a  i-inch 
by  10-inch  test-tube,  add  25  cc.  nitric  acid  (sp.  gr.  1.20).  When 
solution  is  complete  and  all  nitrous  fumes  are  expelled,  add  about 
\  gram  lead  dioxide  and  boil  for  two  minutes,  cool  in  water,  and 
when  settled  compare  color  with  that  of  a  standand  which  has  been 
treated  in  just  the  same  way,  the  manganese  in  the  standard  being 
determined  gravimetrically.  Dilute  the  standard  to  twice  as 
many  cubic  centimeters  as  percentage  of  manganese  and  divide 
cubic  centimeters  of  all  compared  with  it  by  2.  It  takes  some 
time  for  solution  of  pig  iron  and  the  solution  should  be  kept 
over  a  very  low  flame  so  as  not  to  concentrate  bulk  of  solution 
until  solution  is  complete  before  adding  the  lead  dioxide. 


86  /.   C.  Barrett. 

Gravimetric  Method. — Dissolve  5  grams  of  steel  in  60  cc.  nitric 
acid  (sp.  gr.  1.20),  evaporate  to  a  pasty  consistency  in  a  No.  4 
beaker,  then  add  100  cc.  concentrated  nitric  acid,  heat  to  boil- 
ing, and  precipitate  manganese  dioxide  with  potassium  chlorate; 
filter  on  asbestos  and  proceed  as  with  manganese  in  ores.  Pig 
iron  is  treated  in  the  same  way  as  for  phosphorus  until  filtering 
into  a  i6-oz.  flask.  For  manganese  it  is  filtered  into  a  No.  4  beaker 
and  evaporated  twice  with  concentrated  nitric  acid  to  a  pasty 
consistency;  then  100  cc.  of  concentrated  nitric  acid  are  added, 
manganese  dioxide  precipitated  with  potassium  chlorate,  and 
the  manganese  dioxide  treated  in  the  same  way  as  in  the  case 
of  steel  or  ores. 

DETERMINATION   OF   CARBON    BY   COMBUSTION. 

The  steel  or  iron  is  dissolved  in  double  chloride  of  potassium 
and  copper  which  is  dissolved  in  the  proportion  of  5  pounds  to 
6  liters  of  water,  and  has  been  filtered  first  through  paper  and 
then  through  asbestos.  5  per  cent,  of  hydrochloric  acid  is 
added  to  this  solution  as  it  is  used.  For  3  grams  of  steel  use 
1 80  cc.  solution.  If  no  stirring  machine  is  at  hand  add  solution 
to  steel  and  stir  frequently  at  first  and  allow  to  stand  over  night  at 
room  temperature.  Then  warm  on  sand-bath,  stirring  frequently 
until  all  copper  is  in  solution.  Cool  and  filter  through  a  boat 
lined  with  asbestos,  made  by  burning  and  grinding  up  in  water, 
decanting  away  the  murky  part,  leaving  the  fine  asbestos,  which 
by  shaking  up  in  a  bottle  with  water  can  be  easily  transferred 
to  a  boat  to  make  the  felt.  The  solution  of  steel  is  filtered  on  felt, 
carefully  washed  with  hydrochloric  acid,  then  warm  water  until 
free  from  hydrochloric  acid  and  copper.  The  boat  with  carbon 
is  dried  at  80°  or  90°  for  one  hour,  then  burned  in  oxygen  in  a 
platinum  tube  which  contains  a  coil  of  platinum  gauze  and  cop- 
per oxide. 

The  combustion  train  is  made  up  as  follows  : 

Drying  and  purifying  jars  filled  with  potash  through  which 
oxygen  passes  to  combustion-tube ;  following  the  combustion- 
tube  is  a  U-tube  filled  on  one  side  with  anhydrous  cuprous 
chloride  and  on  the  other  with  anhydrous  copper  sulphate  ; 
then  a  [j-tube  filled  with  concentrated  sulphuric  acid  to  close 


Ohio  Steel  Company.  87 

the  lower  part  of  the  (].  Following  these  are  the  absorption  bulbs 
(Geissler's  potash  with  drying  tube  between  the  bulbs).  The 
bulbs  are  filled  with  potash  (sp.  gr.  1.35  or  1.40)  and  the 
drying  tube  with  calcium  chloride.  Connected  with  this  is  a 
Liebig  bulb  filled  with  sulphuric  acid  to  trap.  Then  comes  a 
calcium-chloride  tube  used  as  a  protection,  but  not  weighed. 
Great  care  is  used  in  always  keeping  the  potash  bulb  and  the 
calcium-chloride  tube  filled  with  fresh  material.  A  blank  is 
always  run  before  each  day's  series  is  begun,  and  this  must 
agree  with  the  first  wreight  to  within  0.0005  gram.  Where  a  num- 
ber of  combustions  are  to  be  made  the  Geissler  and  L,iebig  bulbs 
are  weighed  and  then  placed  in  train  for  the  next  combustion, 
using  the  weight  from  the  last  one  done  until  the  series  is  finished. 
Test  the  joints  each  time  the  apparatus  is  put  together.  One  of 
the  essential  requirements  for  good  results  is  cleanliness. 

The  tube  is  heated  up  by  lighting  the  burner  nearest  the  absorp- 
tion bulbs  and  then,  with  oxygen  flowing  so  that  bubbles  go  at  the 
rate  of  3  per  second,  each  burner  slowly  in  succession,  until  the 
whole  tube  is  red  hot,  taking  about  ten  minutes.  Keep  red 
hot  for  fifteen  minutes.  Then  cut  off  oxygen  and  apply  suction 
with  bubbles  going  at  the  same  rate  ;  lower  the  flames  for  a  few 
minutes,  then  extinguish  them.  After  suction  has  run  for  a 
half  hour  the  bulbs  are  ready  to  weigh. 

DETERMINATION   OF   SILICON   IN   STEEL. 

5  grams  are  dissolved  in  50  cc.  nitric  acid  (sp.  gr.  1.20)  and  35 
cc.  dilute  sulphuric  acid  (i :  i ) .  Evaporate  in  a  4^-inch  dish  over 
an  Argand  burner  with  watch-glass  cover  until  bumping  begins; 
remove  cover  and  stir  with  rod  until  it  grains  or  cakes.  Dry 
until  copious  fumes  escape.  Cool,  add  about  20  cc.  dilute  hy- 
drochloric acid  and  100  cc.  water.  Heat  until  solution  is  com- 
plete, filter  and  wash  well  with  hydrochloric  acid  and  hot  water, 
burn,  and  weigh. 


XVI.  METHODS  USED  AT  THE  LABORATORY  OF  THE 
CARNEGIE  STEEL  CO.,  DUQUESNE,  PA. 

i 
BY  JAMES  M.  CAMP. 


DETERMINATION  OF  PHOSPHORUS  IN  PIG  IRON  AND  STEEL. 

5  grams  pig  iron  or  steel  are  dissolved  in  60  cc.  nitric  acid 
(sp.  gr.  i. 20)  in  a  i2-cm.  porcelain  dish,  with  watch-glass  cover, 
evaporated  to  dryness  while  covered,  and  heated  over  a  lamp 
without  cover  till  all  acid  fumes  are  driven  off.  When  cool,  dis- 
solve in  30  to  35  cc.  strong  hydrochloric  acid  and  evaporate 
with  watch-glass  cover  till  excess  of  free  acid  is  driven  off,  as 
indicated  by  the  first  appearance  of  insoluble  ferric  chloride  on  the 
bottom  of  the  dish.  This  is  dissolved  by  adding  2  or  3  cc.  of 
strong  nitric  acid  and  the  solution  diluted  with  warm  water  to 
about  75  cc.,  filtered,  and  washed  into  asoo-cc.  flask,  using  the 
2  per  cent,  nitric  acid  wash  water  used  in  washing  the  yellow 
precipitate,  to  remove  the  last  trace  of  iron.  A  slight  excess  of 
strong  ammonia  is  then  added  (about  25  cc.),  and  then  a  slight 
excess  of  strong  nitric  acid  (about  28  cc. ),  till  the  solution  is  a 
clear  amber  color. 

The  solution  is  heated  or  cooled  to  85°  C.  and  75  cc.  ammo- 
nium molybdate  are  blown  in  by  aid  of  a  pipette  ;  the  flask  is  sha- 
ken for  five  minutes  and  allowed  to  stand  till  the  supernatant  liquid 
is  clear.  It  is  then  filtered  through  a  weighed  filter  that  has 
been  dried  at  100°  to  130°  C.  and  weighed  between  watch-glasses. 
The  precipitate  is  washed  with  water  containing  2  per  cent, 
strong  nitric  acid,  dried  for  one  hour,  or,  till  weight  is  constant, 
at  above  temperature,  and  weighed  between  watch-glasses,  i  .63 
per  cent,  of  weight  is  taken  for  phosphorus. 

Ammonium  Molybdate  Solution. — This  is  made  by  dissolving 
225  grams  molybdic  acid  in  a  mixture  of  6oocc.  water  and  4cocc. 
strong  ammonia,  and  adding  this  solution  to  2.5  liters  nitric  acid 
of  i  .20  specific  gravity.  This  is  kept  in  a  warm  place  over  night 
and  is  then  ready  for  use. 


Carnegie  Steel  Company,  Duquesne,  Pa.  89 

DETERMINATION    OF    PHOSPHORUS  IN  ORES. 

The  agate-mortar  sample  is  dried  at  100°  C.  for  one  hour,  al- 
lowed to  cool,  and  5  grams  weighed  off  into  a  i2-cm.  porcelain 
dish  with  watch-glass  cover,  50  cc.  strong  hydrochloric  acid 
added,  and  the  solution  allowed  to  go  to  dry  ness  on  the  sand-bath; 
30  to  35  cc.  strong  hydrochloric  acid  are  added,  warmed,  and  when 
all  is  in  solution  evaporated  till  the  first  appearance  of  insoluble 
ferric  chloride.  This  is  dissolved  by  adding  one  or  two  drops  of 
strong  hydrochloric  acid  and  the  solution  diluted  with  hot 
water  to  about  75  cc.,  and  filtered  into  a  5oo-cc.  flask. 

The  residue  is  burned  and  fused  with  the  mixed  carbonates  of 
potassium  and  sodium,  dissolved  in  hot  water,  acidified  with  hy- 
drochloric acid  and  evaporated  to  dryness  ;  then  moistened  with 
dilute  hydrochloric  acid  (1:2),  diluted,  and  filtered  intothesame 
flask  with  original  filtrate,  keeping  as  concentrated  as  possible. 
(This  gives  the  silica,  perfectly  pure,  of  the  five  grams  of  ore,  on 
the  filter-paper  ready  for  burning  and  weighing.) 

A  slight  excess  of  strong  ammonia  is  now  added  and  then  a 
slight  excess  of  strong  nitric  acid,  and  the  process  continued  in 
the  same  manner  as  for  pig  iron  or  steel. 

To  save  time,  the  above  process  is  modified  as  follows  :  5 
grams  of  the  dried  ore  in  a  i2-cm.  covered  porcelain  dish  are 
boiled  with  50  cc.  strong  hydrochloric  acid  for  about  thirty  min- 
utes, or,  till  the  ore  is  apparently  all  in  solution,  diluted  with  an 
equal  volume  of  water,  and  filtered  into  another  dish  of  the  same 
size.  The  residue  is  burned  and  fused  with  the  mixed  carbo- 
nates, dissolved  in  hot  water,  acidified  with  hydrochloric  acid  in 
the  same  dish  in  which  the  original  solution  was  made,  and  both 
solutions  allowed  to  go  to  dryness  on  the  sand-bath. 

30  cc.  strong  hydrochloric  acid  are  added  to  the  dish  containing 
the  original  filtrate,  and  heated  till  the  excess  of  hydrochloric  acid 
is  driven  off  ;  dilute  and  filter  into  a  5oo-cc.  flask.  The  fusion 
is  moistened  with  dilute  ttydrochloric  acid,  diluted,  and  when 
in  solution  filtered  into  the  same  flask  with  the  last  filtrate.  The 
process  is  then  carried  on  as  before. 

DETERMINATION  OF  IRON  IN    ORES. 

i  gram  of  the  agate-mortar  sample  dried  at  100°  C.  is  weighed 


90  James  M.   Camp. 

off  into  a  No.  o  beaker  with  watch-glass  cover,  20  cc.  of  strong 
hydrochloric  acid  added,  and  for  a  60  per  cent,  ore  5  cc.  of  the 
stannous  chloride  solution,  heated  on  the  sand-bath  till  all  is  in 
solution  and  the  residue  is  white.  While  still  hot  in  the  same 
beaker,  add  cautiously,  drop  by  drop,  more  stannous  chloride 
solution  till  the  color  due  to  the  presence  of  ferric  chloride,  has 
entirely  disappeared  and  then  one  drop  in  excess.  Transfer  to 
a  No.  4  beaker  containing  about  300  cc.  cold  water,  add  10 
cc.  mercuric  chloride  solution,  and  stir  ;  allow  to  stand  about  one 
minute,  and  then  titrate  with  potassium  bichromate  solution,  until 
a  drop  of  the  solution  added  to  a  drop  of  potassium  ferricyanide 
solution  on  a  porcelain  plate  shows  no  green  color  on  standing 
one-half  minute.  The  number  of  cubic  centimeters  bichromate 
solution  used  gives  the  percentage  of  iron. 

In  case  the  residue  shows  presence  of  iron  it  is  filtered,  burned, 
and  fused  with  mixed  carbonates,  dissolved  in  water,  and  filtered; 
the  oxide  of  iron  on  the  filter  is  dissolved  in  dilute  hydrochloric 
acid  and  allowed  to  run  into  the  original  solution. 

SOLUTIONS. 

Stannous  Chloride  Solution  is  made  by  dissolving  300  grams  of 
the  salt  in  500  cc.  strong  hydrochloric  acid  and  500  cc.  water  ;  i 
cc.  will  reduce  about  o.i  gram  iron. 

Mercuric  Chloride  Solution  is  made  by  dissolving  50  grams  of  the 
salt  in  i  liter  of  water. 

Potassium  Ferricyanide  Solution  is  made  by  dissolving  about 
0.05  gram  of  the  salt  in  50  cc.  water. 

Potassium  Bichromate  Solution  is  made  by  dissolving  8.9  grams 
of  salt  per  liter  of  water  and  standardizing  with  iron  wire,  stand- 
ard steel  or  ore,  and  diluting  so  that  i  cc.  equals  one  per  cent, 
iron  ;  proving  strength  of  solution  after  dilution  with  the  stand- 
ard steel  or  ore. 

DETERMINATION  OF   MANGANESE  IN   ORES. 

The  agate  mortar  sample  is  dried  for  one  hour  at  ioo°C.,  al- 
lowed to  cool,  and  five  grams  weighed  off  into  a  i2-cm.  porce- 
lain dish  with  watch-glass  cover;  50  cc.  strong  hydrochloric  acid 
are  added  and  the  solution  allowed  to  go  to  dryness  on  the  sand- 
bath. 


Carnegie  Steel  Company,  Duquesne,  Pa.  91 

The  residue  is  moistened  with  dilute  hydrochloric  acid  (1:2), 
diluted,  heated  till  all  is  in  solution  and  filtered  into  a  5oo-cc. 
graduated  flask.  The  residue  is  burned  and  fused  with  five  to 
ten  times  its  weight  of  the  mixed  carbonates  of  potassium  and 
sodium.  If  fusion  shows  presence  of  manganese  it  is  dissolved 
in  hot  water,  acidified  with  hydrochloric  acid,  evaporated  to 
dryness,  taken  up  as  before,  and  filtered  into  the  same  flask  with 
the  original  filtrate. 

The  solution  is  cooled,  diluted  to  the  mark,  and,  with  the  aid 
of  an  exactly  agreeing  pipette,  100  cc.  (equal  to  i  gram  of  ore) 
are  taken  as  many  times  as  desired  into  No.  4  beakers.  30  cc. 
strong  nitric  acid  are  added,  and  the  solution  evaporated  to  small 
bulk  (10  to  15  cc.).  75  cc.  strong  nitric  acid  are  now  added  and 
the  solution  heated  to  boiling,  and,  while  boiling,  an  excess  of 
potassium  chlorate  is  added  in  small  portions  and  boiled  a  few 
minutes  after  the  final  puff. 

The  solution  is  cooled  and  filtered  through  a  purified  asbestos 
plug  with  the  aid  of  suction.  Beaker  and  plug  are  washed  twice 
with  strong  nitric  acid  and  plug  blown  back  into  beaker  in  which 
precipitation  was  made.  The  filtering  tube  is  washed  off  with 
water  and  dilute  hydrochloric  acid,  to  dissolve  any  adhering 
precipitate ;  25  cc.  strong  hydrochloric  acid  are  added ;  and 
then  i  to  2  cc.  dilute  sulphuric  acid  added  to  precipitate  any 
barium  that  may  be  present.1  The  solution  is  heated  to  boiling, 
keeping  the  beaker  constantly  agitated  to  avoid  bumping  and 
when  all  the  manganese  dioxide  is  dissolved,  filtered  into  asoo-cc. 
flask  from  the  suspended  asbestos. 

The  solution  is  neutralized  with  ammonia  till  a  faint  perma- 
nent precipitate  of  ferric  hydroxide  is  formed,  10  to  15  cc.  of  a 
25  per  cent,  solution  of  ammonium  acetate  added,  and  the  solution 
heated  to  boiling  and  set  aside  to  settle.  It  is  next  filtered  into 
a  500- cc.  flask  with  the  aid  of  suction,  and  flask  and  funnel 
washed  once  with  hot  water.  The  precipitate  is  dissolved  in  dilute 
hydrochloric  acid,  into  the  same  flask  in  which  the  precipitation 

lAt  this  stage  of  the  analysis,  if  there  is  baryta  in  the  ore,  which  is  usually  the  case, 
the  nitrate  being  very  insoluble  in  strong  nitric  acid,  may  be  precipitated  ;  conse- 
quently it  will  be  filtered  off  with  the  manganese  dioxide,  and  will  ultimately  go 
into  solution  in  the  subsequent  dilution  and  boiling  with  hydrochloric  acid.  This  must 
be  separated  by  addition  of  sulphuric  acid,  and  sufficient  time  allowed  to  precipitate,  or 
it  will  be  weighed  with  the  manganese  as  pyrophosphate. 


92  James  M.   Camp. 

was  made,  and  a  second  basic  acetate  precipitation,  made  as 
before,  filtered  into  the  same  flask  containing  the  first  basic  ace- 
tate filtrate,  and  the  flask  and  funnel  washed  twice  with  hot  water. 

The  subsequent  precipitation  can  be  made  in  the  flask,  or  the 
united  filtrates  are  transferred  to  a  No.  6  beaker,  carefully 
rinsing  out  the  flask,  and  10  cc.  acetic  acid  added.  The  solution 
is  heated  to  boiling,  5  to  10  grams  ammonium  phosphate 
crystals  added,  and  the  solution  stirred  till  the  precipitate  as- 
sumes the  well-known  crystalline  form.  25  cc.  strong  ammonia 
are  now  added  and  the  solution  stirred  for  a  few  minutes  till  the 
precipitate  is  all  crystalline,  and  set  aside  to  settle.  It  is  now 
filtered  through  an  n-cm.  filter-paper  by  aid  of  suction  and 
washed  with  hot  water,  burned,  and  weighed  as  Mn2P2O7.  38.74 
per  cent,  of  its  weight  is  manganese. 

When  only  a  single  determination  is  required,  one  gram  can  be 
weighed  off  and  treated  as  directed  for  five  grams.  But  if 
several  are  to  be  made  and  the  residue  fused,  which  should  be 
done  in  all  cases,  unless  absolutely  certain  that  it  contains  no 
manganese  (as  a  silicate  of  manganese  exists  that  looks  and 
burns  perfectly  white) ,  then  it  is  preferable  to  start  with  five 
grams  as  directed. 

DETERMINATION  OF  MANGANESE  IN  STEEL  AND  PIG  IRON. 

From  2  to  5  grams  of  the  steel  or  pig  iron  are  weighed 
off  into  a  No.  4  beaker  with  watch-glass  cover,  the  least  amount 
necessary  of  nitric  acid  of  1.20  specific  gravity  for  complete  solu- 
tion added,  and  heated  to  boiling.  When  all  is  in  solution  the 
watch-glass  cover  is  removed  and  the  solution  evaporated  over  the 
lamp  till  the  excess  of  nitric  acid  is  driven  off,  as  indicated  by 
the  first  appearance  of  the  insoluble  nitrate  of  iron  in  the  solu- 
tion ;  75  cc.  strong  nitric  acid  are  added,  the  solution  heated 
to  boiling,  and  while  boiling  an  excess  of  potassium  chlorate 
is  added  in  small  portions  and  boiled  a  few  minutes  after  the  final 
puff.  Cool,  and  filter  through  a  purified  asbestos  plug  with 
the  aid  of  suction;  the  beaker  and  plug  are  washed  twice  with 
strong  nitric  acid  and  the  washings  returned  to  the  beaker  in  which 
the  precipitation  was  made.  The  filtering  tube  is  washed  off  with 
water  and  dilute  hydrochloric  acid,  to  dissolve  any  adhering 


Carnegie  Steel  Company,  Duquesne,  Pa.  93 

precipitate,  an  excess  of  strong  hydrochloric  acid  added,  and 
the  solution  heated  to  boiling  till  the  manganese  dioxide  is  all 
in  solution.  It  is  then  filtered  from  the  suspended  asbestos  and 
the  analysis  finished  in  the  same  manner  as  for  manganese  in 
ores. 

In  case  of  a  pig  iron  high  in  silicon,  it  is  preferable  to  dissolve 
in  hydrochloric  acid,  evaporate  to  dry  ness  to  separate  silica, 
moisten  with  dilute  hydrochloric  acid,  dilute,  and  filter.  To  the 
filtrate,  add  an  excess  of  strong  nitric  acid  (at  least  75  cc.,  if  5 
grams  of  iron  were  taken),  and  evaporate  to  total  expulsion  of 
hydrochloric  acid.  75  cc.  strong  nitric  acid  are  added  and  the 
solution  heated  to  boiling.  While  boiling,  an  excess  of  potas- 
sium chlorate  is  added,  and  the  analysis  finished  in  the  same 
manner  as  for  manganese  in  steel. 

DETERMINATION  OF  MANGANESE    BY  COLOR. 

0.2  gram  pig  iron  or  steel,  and  standard  steel  of  known  man- 
ganese content,  are  weighed  off  in  i-inch  by  lo-inch  test-tubes; 
30  cc.  nitric  acid  of  1.20  specific  gravity  are  added  to  each,  the 
tube  heated  over  an  Argand  burner  till  dissolved,  and  boiled  till  all 
the  nitrous  fumes  are  driven  off.  While  boiling,  about  one 
gram  lead  peroxide  is  added,  boiling  continued  for  one 
minute,  and  test-tubes  set  in  a  cold  water-bath  to  settle.  When 
cool,  and  the  supernatant  liquid  is  clear,  the  tube  containing 
the  standard  solution  is  decanted  into  one  of  the  comparing 
tubes  ;  this  can  be  very  safely  done  without  losing  more  than  a 
drop  of  the  solution,  and  without  a  particle  of  the  lead  peroxide 
entering  the  comparing  tube.  The  solution  is  then  diluted  to 
twice  the  number  of  cubic  centimeters,  the  standard  steel  contains 
hundredths  per  cent,  manganese,  and  mixed  thoroughly .  The  test 
pig  iron  or  steel  is  decanted  in  like  manner  into  the  other  com- 
paring tube,  and  diluted  with  cold  water  to  like  colors.  One- 
half  the  reading  in  cubic  centimeters  represents  hundredths 
per  cent,  manganese. 

In  case  the  manganese  is  high  in  the  sample — 0.75  per  cent, 
and  upwards — the  test  and  standard  are  each  boiled  two  minutes 
after  the  addition  of  the  lead  peroxide, — otherwise  the  treatment 
is  the  same. 


94  James  M.   Camp. 

DETERMINATION  OF  SILICON  IN  PIG  IRON. 

Twice  the  factor  weight  (0.9404  gram  of  the  drillings)  is 
weighed  off  into  a  i2-cm.  porcelain  dish,  and  25  cc.  of  the  mixed 
acids,  nitric  and  sulphuric,  mixed  in  the  proportion  of  18  cc.  nitric 
acid  (sp.  gr.  1.20)  and  7  cc.  dilute  sulphuric  acid  (i  :  i)  added, 
heated  over  an  Argand  burner  till  all  is  in  solution,  and  afterwards 
to  dryness,  and  finally  until  dense  white  fumes  of  sulphur  tri- 
oxide  are  given  off.  It  is  then  allowed  to  cool,  moistened  with 
dilute  hydrochloric  acid  (i  :  2),  diluted  with  hot  water,  and 
warmed  till  all  is  in  solution;  filtered,  washed  with  hot  water  and 
dilute  hydrochloric  acid  till  free  from  iron,  burned,  and  \veighed. 
One-half  the  weight  in  decimilligrams  is  hundredths  per  cent,  of 
silicon. 

DETERMINATION  OF  SULPHUR  IN  PIG  IRON  AND  STEEL. 

Aqua  Regia  Method. 

5  grams  of  pig  iron  or  steel  are  weighed  off  into  a  No.  5  beaker, 
with  a  watch-glass  cover,  and  50  cc.  aqua  regia  added  at  one  time. 
This  is  freshly  made  up,  by  mixing  45  cc.  strong  nitric  acid  to  5  cc. 
strong  hydrochloric  acid.  When  the  violent  action  has  ceased, 
heat  is  applied  till  all  is  in  solution,  and  the  solution  evapora- 
ted ,  still  covered ,  until  its  bulk  is  considerably  reduced .  An  excess 
of  strong  hydrochloric  acid  is  then  added  (about  40  cc.)  to  dis- 
place all  the  nitric  acid,  and  the  solution  after  continued  evapo- 
ration is  finally  transferred  to  a  i2-cm.  porcelain  dish,  and  al- 
lowed to  go  to  dryness  on  the  steam-bath.  35  cc.  strong  hydro- 
chloric acid  are  added  and  warmed  till  all  is  in  solution  and 
evaporated  till  the  free  hydrochloric  acid  is  driven  off,  as  indi- 
cated by  a  film  of  ferric  chloride  floating  on  the  surface.  This 
is  dissolved  by  a  drop  or  two  of  strong  hydrochloric  acid,  di- 
luted to  about  75  cc.,  and  filtered  into  a  No.  2  beaker,  washing 
with  hot  water  and  the  least  amount  necessary  of  dilute  hydro- 
chloric acid  to  remove  the  last  trace  of  iron.  Heated  nearly  to 
boiling,  10  cc.  of  a  5  per  cent,  solution  of  barium  chloride  are 
added,  and  the  solution  set  on  a  sand-bath  and  evaporated  to 
the  separation  of  the  insoluble  ferric  chloride  as  before. 

This  is  dissolved  with  a  drop  or  two  of  strong  hydrochloric 


Carnegie  Steel  Company,  Duquesne,  Pa.  95 

acid,  and  with  a  wash-bottle  a  strong  stream  of  cold  water  is 
blown  into  the  beaker,  thoroughly  stirring  up  the  solution  till 
its  volume  is  about  175  cc.  and  set  aside  in  a  cool  place  over 
night.  The  solution  is  filtered  through  a  double  y-cm.  filter, 
washed  with  hot  water  and  dilute  hydrochloric  acid  till  free 
from  iron,  burned  in  an  open  crucible,  and  weighed.  13.756 
per  cent,  of  its  weight  is  sulphur. 

DETERMINATION  OF  SULPHUR  IN  PIG  IRON  AND  STEEL. 

Iodine  Method. 

5  grams  of  pig  iron  or  steel  are  weighed  off  into  a  dry  5oo-cc. 
flask,  provided  with  a  doubly  perforated  rubber  stopper,  with  a 
long-stem  4-oz.  funnel-tube  with  a  stop-cock,  and  a  delivery-tube 
bent  at  right  angles,  on  which  a  short  piece  of  -^-inch  rubber 
tubing  is  placed,  making  connection  with  a  delivery- tube  also 
bent  at  right  angles,  reaching  to  the  bottom  of  a  i-inch  by  10- 
inch  test-tube,  suitably  supported.  About  10  cc.  of  the  ammo- 
niacal  solution  of  cadmium  chloride  are  introduced  into  the  test- 
tube,  which  is  diluted  with  cold  water  until  the  tube  is  about 
two-thirds  full.  80  cc.  of  dilute  hydrochloric  acid  (1:2)  are 
poured  into  the  funnel-tube,  a  file  mark  on  the  bulb  indicating 
this  amount,  which  is  allowed  to  run  into  the  flask.  The  stop- 
cock is  then  closed  and  a  gentle  heat  applied,  till  the  drillings 
are  all  in  solution,  and  the  flask  is  then  strongly  heated  until 
nothing  but  steam  escapes  from  the  delivery-tube. 

The  apparatus  is  then  disconnected,  and  the  delivery-tube  is 
placed  in  the  No.  4  beaker  in  which  the  titrations  are  made;  the 
contents  of  the  test-tube  are  then  poured  into  the  beaker,  the 
test-tube  filled  to  the  top  twice  with  cold  water,  the  sides  of  the 
tube  rinsed  down  with  about  25  cc.  dilute  hydrochloric  acid,  and 
filled  again  with  cold  water.  The  total  volume  of  the  solution 
equaling  about  400  cc.  (both  acid  and  water  are  supplied  from 
overhead  aspirator  bottle  and  suitable  rubber  connections  with 
pinch-cocks) ,  the  delivery-tube  is  now  rinsed  off  inside  and  out 
with  dilute  hydrochloric  acid,  and  about  5  cc.  starch  solution 
added  to  the  beaker. 

Without  waiting  for  complete  solution  of  the  cadmium  sul- 
phide, the  iodine  solution  is  run  in  from  a  burette,  stirring 


96  James  M.   Camp. 

gently,  till  a  blue  color  is  obtained.  The  solution  is  then  stirred 
vigorously,  keeping  a  blue  color  by  fresh  additions  of  the  iodine 
solution,  till  the  precipitate  of  cadmium  sulphide  is  all  dissolved, 
and  the  proper  permanent  blue  color  is  obtained.  The  amount 
of  iodine  solution  used  in  cubic  centimeters  represents  hun- 
dredths  per  cent,  sulphur. 

The  Iodine  Solution  is  made  by  placing  in  a  dry  5oo-cc. 
flask  about  35  grams  potassium  iodide,  16  grams  iodine,  and  50  cc. 
water ;  shake,  and  dilute  cautiously  until  all  is  in  solution  ; 
and  finally  dilute  to  3.5  liters.  This  is  standardized  with  steels 
of  known  sulphur  content,  so  that  i  cc.  equals  0.0005  gram  sul- 
phur. 

The  Cadmium  Chloride  Solution  is  madeb}'  dissolving  100  grams 
cadmium  chloride  in  i  liter  of  water,  adding  500  cc.  strong  ammo- 
nia, and  filtering  into  an  8-liter  bottle.  Two  liters  of  water  are 
now  added,  and  the  bottle  filled  to  the  8-liter  mark  with  strong 
ammonia. 

The  Starch  Solution  is  made  by  adding  to  one-half  gallon  boiling 
water,  in  a  gallon  flask,  about  25  grams  pure  wheat  starch,  pre- 
viously stirred  up  into  a  thin  paste  with  cold  water  ;  this  is 
boiled  ten  minutes  and  about  25  grams  pure  granulated  zinc 
chloride  dissolved  in  water  added,  and  the  solution  diluted  with 
cold  water  to  the  gallon  mark.  The  solution  is  mixed,  allowed 
to  settle  over  night,  and  the  clear  solution  decanted  into  a  glass- 
stoppered  bottle  for  use. 

This  solution  will  keep  indefinitely. 

DETERMINATION  OF  NICKEL  IN  STEEL. 

Our  determinations  of  nickel  are  made  exclusively  in  machin- 
ery steel,  pinions,  and  rolls  ;  the  amount  ranges  from  2.5  to  3.5 
per  cent.  No  attempt  is  made  to  separate  cobalt,  as  it  seldom 
occurs  in  the  steel,  and  when  present  is  derived  from  the  nickel 
ores  in  inconsiderable  amounts.  The  method  is  as  follows  : 

Dissolve  i  gram  of  steel  in  15  cc.  nitric  acid  (sp.  gr.  1.20),  in 
a  No.  3  beaker,  transfer  to  a  liter  flask  and  dilute  with  hot 
water  to  about  700  cc.  Neutralize  the  excess  of  acid  with  am- 
monia, and  add  about  15  grams  sodium  acetate  in  crystals.  Heat 
to  boiling  and  boil  one-half  minute;  allow  precipitate  to  subside, 


Carnegie  Steel  Company,  Duqueme,  Pa.  97 

and  filter  through  an  u-inch  fluted  filter,  into  a  large  beaker. 
Drain  precipitate  thoroughly,  perforate  filter,  and  wash  precipi- 
tate back  into  flask  in  which  precipitation  was  made,  wash  filter 
with  dilute  hydrochloric  acid  and  water  till  free  from  iron; 
add  a  slight  excess  of  hydrochloric  acid  to  flask  to  dissolve  all 
the  precipitate,  and  dilute  to  about  700  cc.  Neutralize  and 
make  second  basic  acetate  precipitation  and  filtration  as  before. 

Unite  filtrates,  make  faintly  ammoniacal,  and  heat  nearly  to 
boiling.  If  traces  of  iron  separate,  filter ,  and  in  filtrate  pass 
hydrogen  sulphide  till  the  solution  smells  strongly  of  the  gas. 
Make  slightly  acid  with  acetic  acid,  testing  with  litmus  paper, 
and  set  on  steam-bath  till  the  precipitate  of  nickel  sulphide  sub- 
sides. Filter,  wash  with  hot  water,  burn  in  the  hottest  part  of 
the  muffle,  and  weigh  as  NiO.  78.58  per  cent,  of  its  weight  is 
nickel. 

In  case  copper  is  present  in  any  appreciable  amount,  dissolve 
the  precipitate  of  nickel  sulphide  in  hydrochloric  acid  with  the 
aid  of  potassium  chlorate,  filter  from  the  paper,  dilute,  warm, 
precipitate  the  copper  with  hydrogen  sulphide,  let  subside,  filter, 
wash,  and  if  desired  burn  and  weigh.  To  the  filtrate  add  am- 
monia in  slight  excess,  pass  hydrogen  sulphide,  let  precipitate 
subside,  filter,  wash,  burn,  and  weigh  as  NiO,  as  before. 

DETERMINATION  OF  CARBON  IN  STEEL  BY  COMBUSTION. 

From  i  to  10  grams  of  steel  are  weighed  off  into  a  dry  beaker 
of  suitable  size,  and  from  TOO  cc.  to  500  cc.  of  the  double  chlo- 
ride of  copper  and  potassium  solution  added.  This  is  made 
by  dissolving  5  pounds  of  the  double  chloride  of  copper  and  po- 
tassium in  five  liters  of  water,  filtering  through  a  puri- 
fied asbestos  plug,  and  adding  250  cc.,  or  5  per  cent., 
strong  hydrochloric  acid.  The  beaker  is  placed  on  a  suit- 
ably arranged  stirring  apparatus,  making  about  250  revolu- 
tions per  minute,  and  kept  at  a  temperature  of  about  50°  C.  till 
all  is  in  solution.  When  permissible  it  is  preferred  to  allow  the 
solution  to  cool,  and  the  carbonaceous  residue  to  subside  before 
filtering.  The  solution  is  then  filtered  through  a  perforated 
platinum  boat,  with  suitable  asbestos  blanket,  and  washed  once 
with  dilute  hydrochloric  acid,  and  then  with  warm  water,  allowing 


98  James  M.   Camp. 

all  the  washings  to  run  from  the  beaker  into  the  boat.  The  boat 
is  then  dried  at  about  85°  C.  and  is  finally  transferred  to  the 
platinum  combustion-tube. 

The  accompanying  photograph  shows  the  arrangement  of  the 
apparatus.  In  front  of  the  combustion  furnace  C  is  the  double 
purifying  train  for  oxygen  and  air  ;  the  first  tubes,  A  and  A', 
contain  a  strong  solution  of  caustic  potash  of  1.4  specific  grav- 
ity. Solution  of  this  strength  is  also  used  in  the  potash  bulbs. 
Tubes  B  and  B'  are  filled  to  the  top  with  stick  caustic  potash  in 
short  pieces.  These  tubes  are  connected  by  means  of  a  three- 
way  tube,  with  suitably  arranged  stop-cocks  and  rubber  tubing, 
with  the  platinum  combustion-tube,  resting  in  a  lo-burner  fur- 
nace C.  The  tube  is  f  of  an  inch  in  inside  diameter  and  17 
inches  long,  provided  with  a  gas-tight  joint,  and  prolongations 
6  inches  long  and  -£$  inch  internal  diameter.  2  inches  from 
the  rear  end  of  the  tube  is  placed  a  coil  of  platinum  gauze  2 
inches  long  completely  filling  the  tube,  then  2  inches  of 
coarse  lump  oxide  of  copper,  and  2  inches  more  of  platinum 
gauze. 

Next  to  the  combustion-tube  comes  the  6-inch  purifying  [)-tube 
D,  the  first  half  of  which  is  filled  with  granulated  anhydrous 
cuprous  chloride  and  the  second  half  with  anhydrous  copper 
sulphate.  After  this  comes  the  special  (j-tube  E,  contain- 
ing about  10  cc.  strong  sulphuric  acid.  The  last  half  of  the 
tube  contains  broken  glass  rods  to  diminish  the  air  space.  Then 
comes  the  potash  bulb  B,  with  a  drying  tube  with  ground-glass 
joint,  and  filled  with  freshly  burned  calcium  chloride.  After 
this  a  potash  bulb  G,  containing  strong  sulphuric  acid,  and 
lastly  the  safety-tube  H,  filled  with  calcium  chloride. 

It  will  be  observed  that  sulphuric  acid  is  used  as  a  drying 
medium  both  before  and  after  the  potash  bulb,  as  the  writer 
doubts  the  practicability  of  constantly  moistening  the  gases  to 
the  proper  degree  with  a  plug  of  moist  cotton,  and  prefers  rather 
to  dry  the  gases  perfectly  before  entering  the  absorption-tube, 
and  by  means  of  the  sulphuric-acid  tube  to  catch  any  moisture 
taken  up  from  the  potash  bulb,  which  will  be  weighed  and  its 
gain  added  to  the  gain  of  the  potash  bulb. 

The  combustion  is  proceeded   with  as  follows  :      After   the 


l -35 


ioo  Carnegie  Steel  Company,  Duquesne,  Pa. 

introduction  of  the  boat  into  the  combustion- tubes,  the  oxygen 
is  started  flowing  through  the  apparatus  at  the  rate  of  three  bub- 
bles per  second  in  the  potash  bulb.  The  burners  under  the 
platinum  gauze  and  copper  oxide  are  ignited,  and,  after  the 
tube  has  acquired  a  full  red  color,  the  burners  in  front  of  the 
boat  are  turned  on,  and  finally  those  under  it  until  the  tube 
throughout  is  a  full  red.  This  is  continued  for  fifteen  min- 
utes, then  the  oxygen  is  shut  off,  the  burners  extinguished,  and 
air  is  aspirated  or  forced  through  the  apparatus,  at  the  same 
rate  as  the  oxygen,  for  fifteen  minutes.  The  two  tubes  are 
then  disconnected,  the  small  caps  placed  on  the  ends,  and  each 
of  them  weighed,  the  gain  in  the  tube  containing  the  sulphuric 
acid  being  added  to  the  gain  of  the  potash  bulb.  Three-elevenths 
of  the  total  gain  is  carbon.  These  weights  are  taken  as  the  first 
weights  of  the  succeeding  combustion.  At  the  beginning  of  a 
series  of  combustions,  a  blank  analysis  is  run  to  get  the  first 
weights. 


APPENDIX.1 


BLAST-FURNACE  CINDERS  AND  THEIR  ANALYSIS.2 


BY  JAMES  M.  CAMP, 

Chemist  to  the  Carnegie  Steel  Company,  Duquesne,  Pa. 

It  is  the  object  of  this  paper  to  deal  exclusively  with  the  cin- 
der made  in  furnaces  making  Bessemer  iron,  for  the  reason  that 
this  iron  is  almost  exclusively  the  product  of  the  furnaces  of 
this  region,  the  largest  producers  and  consumers  of  the  world 
being  found  here  ;  and  also  for  the  reason  that  the  writer's  ex- 
perience has  been  particularly  confined  to  that  field.  On  account 
of  the  easy  solubility  of  cinders,  and  the  simplicity  of  the  analy- 
sis in  general,  this  paper  is  dedicated  to  those  who  know  noth- 
ing of  the  subject.  In  it  they  will  find  much  that  is  old  and, 
possibly,  some  few  things  that  are  new. 

In  the  analysis  of  cinder,  like  many  others,  it  is  of  prime 
importance  that  the  results,  to  be  of  service  to  the  furnace  mana- 
ger, be  obtained  quickly.  Consequently,  the  methods  used  are 
those  yielding  the  quickest  results  with  the  maximum  accuracy, 
the  trifling  errors,  due  to  the  rapid  manipulation,  being  offset 
by  variations  in  each  cinder  flush,  and  variations  from  flush  to 
flush.  This  difference  is  due  to  several  causes,  chief  among 
which  are  the  following  : 

i st.  Changes  in  the  burden,  due  to  variations  in  the  weights 
of  ore  or  flux.  2d.  Variations,  more  or  less  great,  in  the  ore, 
flux,  or  fuel,  which  the  method  or  time  of  sampling  will  not 
show.  3d.  Most  important,  and  ever  varying  changes,  due  to 
the  reduction  of  more  or  less  silica  to  silicon  in  the  hearth,  and 
its  consequent  absorption  by  the  iron  and  loss  to  the  cinder. 
This  latter  change  is  due  to  the  variation  in  the  temperature  of 
the  hearth,  and  may  be  caused  by  (i)  a  reduction  of  the  bur- 

1  Additional  methods  which  have  been  contributed  by  chemists  of  the  Pittsburg  re- 
gion to  the  transactions  of  the  Chemical  Section  of  the  Engineers'  Society  of  Western 
Pennsylvania. 

2  Read  before  the  Chemical  Section  of  the  Engineers'  Society  of  Western  Penn- 
sylvania, January  21,  1897. 


IO2  James  M.  Camp. 

den,  (2)  extra  coke,  or,  as  is  commonly  called,  a  black  charge, 
(3)  to  a  higher  or  lower  temperature  of  blast,  (4)  a  slip  in  the 
furnace  with  the  resulting  introduction  of  cold  stock  into  the 
hearth,  (5)  to  a  reduction  in  the  volume  of  air  forced  into  the 
furnace,  with  its  resulting  concentration  of  heat  at  the  hearth, 
and  (6)  changes  in  the  moisture  content  of  the  air.  As  a  conse- 
quence of  the  above  changes,  sometimes  working  in  unison,  and 
again  at  variance  with  each  other,  the  production  of  cinder 
within  certain  close  limits,  is  an  unsolved  problem.  The  writer 
has  known  one  or  two  instances,  when  the  cinder  of  two  con- 
secutive days  showed  exactly  the  same  silica,  but  the  laboratory 
was  credited  with  this  fine  piece  of  metallurgical  work.  In  the 
selection  of  samples,  individual  flushes  are  sometimes  analyzed 
to  represent  the  day's  work,  but  the  practice  is  bad,  for  the  rea- 
sons given  above,  and  it  is  preferable  to  sample  each  flush  dur- 
ing the  day  of  twenty-four  hours.  This  is  usually  done  by  one 
of  the  furnace  employees,  by  breaking  equal-sized  pieces  from 
the  test-mold  samples  taken  during  the  day.  These  samples, 
properly  labeled,  are  delivered  at  the  laboratory  early  in  the 
morning,  and  are  there  crushed  in  an  iron  or  steel  mortar  by  the 
boy  to  whom  this  task  is  allotted,  and  the  entire  sample  passed 
through  a  forty-mesh  sieve.  In  case  the  sample  contains  iron 
in  the  form  of  shot,  these  are  thrown  aside  as  not  being  part  of 
the  cinder.  Only  such  iron  should  be  shown  in  the  analysis  as 
is  present  in  the  form  of  oxide.  Part  of  the  samples,  sufficient 
for  the  analysis,  are  then  placed  in  the  agate  mortar  grinding 
machines,  and  are  there  ground  till,  in  the  judgment  of  the 
analyst,  they  are  sufficiently  fine,  and  the  samples,  after  passing 
a  magnet  through  them  to  separate  any  fine  shot  iron,  are  ready 
for  the  analysis. 

SILICA. 

In  the  determination  of  silica,  or  as  it  is  commonly  called,  in- 
soluble residue,  on  account  of  the  method  of  analysis,  i  gram  of 
the  sample  is  weighed  off  into  an  n-cm.  porcelain  dish,  with 
watch-glass  cover;  10  cc.  water  are  added  and  the  powder 
stirred  up  until  it  is  all  moistened.  10  cc.  of  strong  hydrochloric 
acid  are  now  added,  and  if  the  sample  contains  much  iron,  a 


Blast- Furnace  Cinders  and  their  Analysis.  103 

few  drops  of  nitric  acid,  and  the  solution,  still  covered,  evaporated 
to  dry  ness  over  an  Argand  burner  and  thoroughly  dried.  When 
dry  the  dish  is  allowed  to  cool,  and  the  residue  is  moistened 
with  about  3  cc.  of  strong  hydrochloric  acid,  and  again  evapo- 
rated to  hard  dryness.  This  is  an  essential  point  for  rapid  filtra- 
tion, as  a  single  evaporation,  no  matter  how  well  done,  does  not 
dehydrate  the  silica,  and  a  serious  loss  of  time  may  result  in 
filtering.  The  dish  is  again  allowed  to  cool,  and  the  residue 
taken  up  with  a  mixture  of  20  cc.  strong  hydrochloric  acid  and 
40  cc.  water,  the  large  amount  of  hydrochloric  acid  being 
added  to  form  ammonium  chloride  in  the  subsequent  part  of  the 
operation.  The  dish  and  its  contents  are  heated  to  near  the 
boiling-point  for  a  few  minutes,  and  filtered  through  a  9-cm. 
filter,  washed  with  hot  water  till  free  from  chlorine,  burned  and 
weighed.  The  native  Bessemer  ores  used  at  present  are  practi- 
cally free  from  barium,  consequently  volatilization  of  the  silica 
with  hydrofluoric  acid  is  not  needed. 

The  following  are  some  comparative  results  by  the  above 
method,  and  those  obtained  by  carbonate  fusion,  solution  in 
water,  acidifying  with  hydrochloric  acid,  evaporating  to  dryness 
and  treating  as  usual : 

Insoluble  residue  by  solution.  Silica  by  fusion. 

No.  Per  cent.  Per  cent. 

1  31.09  31.29 

2  31.67  31.65 

3  31-55  31.50 

4  30.47  30.5° 

5  31-75  31-96 

6  29.38  29.50 

7  30-26  30.37 

8  30.37  30.50 

9  3°-74  30.75 
10  31.40  31.34 

IRON  OXIDE  AND  ALUMINA. 

Alumina. — The  filtrate  from  the  silica,  in  a  No.  3  beaker, 
with  a  watch-glass  cover,  is  heated  to  boiling,  and  a  slight  excess 
of  strong  ammonia  added,  and  the  solution  boiled  for  a  few  min- 
utes. The  beaker  is  then  removed  from  the  heat  and  placed  in  a 
cold  water-bath  to  cool  and  for  the  precipitate  to  settle.  When  the 


IO4  James  M.   Camp. 

precipitate  has  settled  completely,  filter  and  wash,  by  decantation 
through  an  n-cm.  filter,  keeping  the  paper  full  until  the  precipi- 
tate is  reached.  Then  let  the  funnel  drain  and  pour  the  precipi- 
tate on  the  filter  with  a  steady  stream  until  the  beaker  is  drained. 
Wash  with  hot  water  until  free  from  chlorine,  burn,  and  weigh 
as  iron  and  aluminum  sesquioxides. 

Iron. — Into  a  No.  2  beaker,  without  lip  and  with  a  watch-glass 
cover,  there  had  been  previously  weighed  off  i  gram  of  the 
original  sample;  to  this  was  added  30  cc.  of  water  and  20  cc. 
of  strong  hydrochloric  acid,  and  set  on  the  steam-bath  to 
dissolve.  This  solution  is  now  boiled  for  a  few  minutes  till 
all  is  dissolved,  and  the  hydrogen  sulphide  all  driven  off.  To 
this,  while  still  hot,  a  slight  excess  of  stannous  chloride  is  added 
(abqut  three  drops),  as  the  iron  is  all  present  in  the  ferrous 
form,  and  the  solution  diluted  with  cold  water  to  about  300  cc. 
10  cc.  of  the  mercuric  chloride  solution  are  now  added,  the  solu- 
tion is  stirred,  and  after  waiting  one  minute  it  is  titrated  with 
potassium  bichromate  solution,  as  previously  described  before  this 
society.1  The  iron  is  reported  as  iron,  but  subtracted  as  sesqui- 
oxide  from  the  iron  oxide  -f-  alumina  obtained  before. 

UME. 

The  filtrate  from  the  alumina  in  a  No.  4  beaker  is  heated  to 
boiling  and  25  cc.  of  a  saturated  solution  of  ammonium  oxalate 
added,  and  10  cc.  of  strong  ammonia.  This  is  boiled  for  a  few 
minutes,  removed  from  the  heat  and  the  precipitate  allowed  to 
settle.  It  is  then  filtered  through  an  n-cm.  filter,  washed  with 
hot  water  till  free  from  chlorine,  and  burned  in  a  muffle  furnace, 
allowed  to  cool  in  a  desiccator,  and  weighed  as  lime.  The  heat 
of  a  muffle  furnace,  at  an  ordinary  red  heat,  will  thoroughly  de- 
compose calcium  oxalate,  for  in  no  other  case  after  treating  as 
above,  and  then  heating  at  the  highest  temperature  of  the  blast- 
lamp,  was  there  found  a  greater  difference  than  1.2  per  cent. 
In  case  the  cinder  is  high  in  magnesia,  due  to  the  use  of  all  or 
part  dolomite  as  a  flux,  a  double  precipitation  is  made  of  the 
lime  as  oxalate. 

1  Transactions  Engineers*  Society  Western  Penna.,   Vol.  XI. 


Blast- Furnace  Cinders  and  their  Analysis.  105 

MAGNESIA. 

The  filtrate  from  the  lime,  which  need  not  exceed  400  or  500 
cc.,  in  a  No.  5  beaker,  is  cooled  by  placing  it  in  a  cold  water- 
bath,  and  slightly  acidulated  with  hydrochloric  acid,  about  5  cc. 
For  a  cinder  containing  not  over  8  per  cent,  of  magnesia,  10  cc. 
of  a  10  per  cent,  solution  of  sodium  phosphate  are  added,  and 
gradually  from  a  measure,  with  constant  stirring,  50  cc.  of  strong 
ammonia.  Stir  thoroughly  and  at  intervals  for  two  or  three 
hours,  then  filter,  wash  with  dilute  ammonia  (1:3)  till  free 
from  chlorine,  burn,  and  weigh. 

MANGANESE. 

The  behavior  of  manganese  in  the  furnace  is  similar  to  that  of 
silicon.  The  higher  the  heat  the  more  of  the  oxides  are  reduced 
and  alloy  with  the  iron,  and  per  contra,  the  lower  the  heat,  the 
less  are  reduced,  and  remain  in  the  cinder.  In  the  method  de- 
tailed above  no  attention  has  been  paid  to  this  element,  part  of 
the  manganese  being  weighed  with  the  oxide  of  iron  and 
alumina,  and  part  with  the  lime.  The  amount  in  the  cinder  is, 
as  a  rule,  low,  and  the  trifling  error  introduced  does  not  affect 
the  metallurgical  value  of  the  results.  Many  determinations 
have  been  made,  by  the  writer,  of  manganese  in  the  iron  and 
alumina  and  lime  precipitates,  as  determined  above,  and  in 
separate  samples  of  the  cinder,  with  the  object  of  finding  a  rule 
whereby  a  certain  amount  of  the  total  could  be  deducted  from 
each,  but  without  avail.  And  in  case  an  accurate,  complete 
analysis  is  desired,  instead  of  an  ammonia  precipitation  of  the 
iron  and  alumina,  a  double  basic  acetate  precipitation  must  be 
made,  and  the  manganese  precipitated  in  the  united  filtrates 
with  bromine,  before  precipitating  the  lime.  For  some  time  past 
the  writer  has  been  using  the  colorimetric  method  on  cinders, 
exactly  as  it  is  used  for  the  determination  of  manganese  in  pig 
iron  and  steel,  with  very  satisfactory  results. 

Herewith  are  given  some  comparative  results,  using  the  color- 
imetric method  and  those  obtained  by  the  potassium  chlorate 
method  : 


io6  James  M.   Camp. 

Colorimetric.  Potassium  chlorate. 

No.  Per  cent.  Per  cent. 

1  0.40  0.42 

2  0,41  0.40 

3  0.31  0.29 

4  0.35  0.33 

5  0.47  0.48 

6  0.23  O.22 

7  0.27  0.26 

8  0.30  0.31 

9  0.33  0.32 
10  0.36  0.36 

SULPHUR. 

A  blast-furnace  cinder  will  contain  practically  all  the  sulphur 
of  the  ore,  flux  and  fuel,  less  the  amount  contained  in  the  iron, 
which  amount  is  dependent  on  the  temperature  of  the  hearth. 
The  higher  the  temperature  the  lower  the  sulphur,  and  vice  versa. 
Cinders  will  vary  in  sulphur  under  normal  conditions  of  ore  and 
fuel,  from  i  to  2  per  cent.,  depending  on  the  proportion  of 
cinder  produced  to  the  ton  of  iron.  The  determination  is 
effected  as  follows  :  Into  a  dry  half-liter  flask,  introduce  about 
\  inch,  equal  to  about  5  grams  of  chemically  pure  stick  zinc, 
and  then  0.25  gram  of  the  cinder.  The  flask  is  provided  with  a 
doubly  perforated  rubber  stopper.  Through  one  opening  a  funnel- 
tube  is  placed,  reaching  to  the  bottom  of  the  flask,  and  through  the 
other  a  short  piece  of  glass  tubing,  bent  at  right  angles,  and 
connected  by  a  short  piece  of  rubber  tubing  to  the  delivery-tube, 
also  bent  at  right  angles,  reaching  to  the  bottom  of  a  i-inch  by 
lo-inch  test-tube,  into  which  about  10  cc.  of  the  ammoniacal 
solution  of  cadmium  chloride  are  introduced,  and  the  test-tube 
filled  about  three-fourths  full  of  cold  water.  10  cc.  of  water  are 
now  added  to  the  flask,  and  gently  shaken  till  the  cinder  is 
moistened,  to  prevent  caking  on  the  bottom..  The  apparatus 
is  connected,  and  50  cc.  of  dilute  hydrochloric  acid  added,  one  of 
acid  to  two  of  water.  The  cinder  is  dissolved  almost  instantly, 
liberating  a  large  volume  of  hydrogen  sulphide. 

The  compact  zinc  dissolves  more  slowly,  liberating  hydrogen, 
which  gradually  displaces  the  hydrogen  sulphide,  and  carries  it 
over  to  the  absorbent.  A  gentle  heat  is  applied,  which  is  grad- 


Blast- Furnace  Cinders  and  their  Analysis.  107 

ually  increased  until  the  zinc  is  dissolved,  and  nothing  but 
steam  escapes  from  the  delivery-tube.  The  apparatus  is  then 
disconnected,  and  the  solution  titrated  with  iodine,  using  the 
same  solution  as  is  used  for  the  determination  of  sulphur  in  iron 
or  steel. 

The  following  are  some  results  obtained  as  described  above 
and  those  obtained  by  fusion  with  the  mixed  carbonates  and  niter 
solution,  evaporation  to  dryness,  solution,  filtering,  and  precipita- 
ting with  barium  chloride  : 

Titrating  with  iodine.  Weighing  as 

The  evolved  hydrogen  sulphide.  barium  sulphate. 

No.  Per  cent.  Per  cent. 

1  1-55  1.56 

2  1.65  1.63 

3  1-57  1-59 

4  1.67  1.69 

5  1-58  1.59 

6  1.93  1.96 

7  1.64  1.62 

8  1.80  1.79 

9  1.82  1.83 
10  1.80  1.82 

PHOSPHORUS. 

Phosphorus,  under  normal  conditions  of  temperature,  is  prac- 
tically all  reduced  in  the  hearth  of  the  furnace,  and  there  com- 
bines with  the  iron,  the  amount  remaining  in  the  cinder  varying 
from  a  trace  up  to  0.02  per  cent.,  the  average  being  much  nearer 
the  former  than  the  latter  figure.  The  determination  is  as  fol- 
lows : 

10  grams  of  the  cinder  are  weighed  off  into  a  i2-cm.  porcelain 
dish  with  a  watch-glass  cover,  and  stirred  up  into  a  paste  with 
water.  50  cc.  of  strong  hydrochloric  acid  are  now  added  and  2 
cc.  of  nitric  acid,  and  the  solution  evaporated  to  hard  dryness. 
The  dish  is  allowed  to  cool  and  then  moistened  with  about  25 
cc.  strong  hydrochloric  acid,  and  again  evaporated  to  hard  dry- 
ness.  When  cool,  from  15  to  20  cc.  strong  hydrochloric  acid 
are  added,  sufficient  to  moisten  the  residue,  and  the  dish  and  its 
contents  warmed  for  a  few  minutes,  and  diluted  with  warm  water 
to  about  100  cc.  This  is  filtered  through  an  ii-cm.  filter  into  a 
half-liter  flask,  and  slightly  washed  with  hot  water.  To  the  fil- 


U2STIV 


io8  Blast- Furnace  Cinders  and  their  Analysis. 

trate  a  slight  excess  of  strong  ammonia  is  added,  about  25  cc., 
and  then  a  slight  excess  of  strong  nitric  acid,  and  the  solution 
heated  to  85°  C.  and  75  cc.  of  ammonium  rnolybdate  solution 
blown  in  by  aid  of  a  pipette.  The  flask  is  shaken  for  about  five 
minutes,  and  the  yellow  precipitate  collected  and  weighed  the 
same  as  in  ores,  pig  iron,  or  steel. 

This  analysis,  like  the  determination  of  alkalies  which  are 
ever  present  in  cinders,  has  no  known  metallurgical  significance, 
for  they  are  beyond  control,  and  are  rarely 'if  ever  determined, 
except  for  the  gratification  of  idle  curiosity,  and  in  a  furnace  and 
steel  works  laboratory  so  much  is  wanted  that  is  essential  to  the 
proper  metallurgical  operation  of  the  plant,  that  scant  time  is 
left  for  work  which  is  not  essential. 


BARIUM  HYDROXIDE  AS  AN  ABSORBENT  IN  CARBON 
DETERMINATIONS. ' 


BY  A.  G.  MCKKNNA, 

Chemist  to  the  Sterling  Steel  Company,  Demmler,  Pa. 

In  the  determination  of  carbon  in  iron  or  steel,  potassium 
hydroxide  has  been  commonly  used  as  an  absorbent  for  the 
carbon  dioxide  formed  by  combustion  of  the  carbonaceous  res- 
idue left  after  treatment  of  the  metal  by  an  appropriate  solvent. 
In  the  somewhat  similar  determination  of  carbon  dioxide  exist- 
ing in  the  atmosphere,  barium  hydroxide  has  been  almost  uni- 
versally employed  as  the  absorbent.  As  the  use  of  the  latter  ab- 
sorbent offers  some  striking  advantages  over  potassium  hydrox- 
ide, the  society  may  be  interested  in  a  number  of  experiments 
showing  what  precautions  are  necessary  if  barium  hydroxide  is 
used  in  the  combustion  method. 

The  apparatus  employed  in  all  the  experiments  consisted  of  a 
platinum  combustion-tube  containing  copper  oxide  and  platinum 
gauze  arranged  as  usual  to  insure  complete  oxidation  of  the  car- 
bon to  carbon  dioxide  with  the  customary  means  for  purifying 
the  current  of  oxygen  and  air  from  carbon  dioxide  before  enter- 
ing the  tube.  The  barium  hydroxide,  to  absorb  the  products  of 
the  combustion,  was  contained  in  an  absorption- tube  consisting 
of  a  series  of  ten  bulbs  as  shown  in  the  sketch. 

In  the  first  experiments  the  fixed  carbon  from  a  coke  was  used 
as  a  material  for  combustion.  A  known  amount  was  weighed 
into  a  platinum  boat  which  was  then  inserted  into  the  tube. 
The  absorption-tube  containing  100  cc.  of  a  solution  of  barium 
hydroxide  of  known  strength  was  next  attached  directly  to  the 
combustion-tube  through  which  a  slow  current  of  oxygen  was 
forced.  The  burners  were  now  lighted  in  the  usual  order  and 
the  combustion  continued  for  fifteen  minutes,  at  the  end  of  which 
time  the  burners  were  extinguished,  but  the  current  of  oxygen 
was  continued  for  another  fifteen  minutes  in  order  to  carry  all 
carbon  dioxide  into  the  absorption- tube.  The  tube  was  now 

i  Read  before  the  Chemical  Section  of  the  Engineers'  Society  of  Western  Pennsylva- 
nia, March  15,  1895. 


no  A.   G.  McKenna. 

disconnected  and  its  contents  filtered  into  a  flask,  using  a  gentle 
suction  so  as  to  bring  as  little  air  as  possible  in  contact  with  the 
solution.  In  washing  it  was  found  necessary  to  free  the  wash 
water  from  carbon  dioxide  by  boiling  just  previous  to  use.  The 
filtrate  in  the  flask  was  now  titrated  with  standard  sulphuric 
acid,  using  phenol-phthalein  as  an  indicator.  The  end-point  is 
remarkably  sharp  and  distinct.  The  sulphuric  acid  used  was 
•^  normal,  in  which  i  cc.  —  0.0003  gram  carbon.  If  the  bar- 
ium hydroxide  solution  is  also  made  ^\  normal,  the  difference  be- 
tween loo  cc.  and  the  number  of  cubic  centimeters  of  sulphuric 
acid  used  in  the  titration  multiplied  by  0.3  will  give  the  milli- 
grams of  carbon  in  the  sample. 

If  the  barium  hydroxide  is  stronger  or  weaker  it  is  simply 
necessary  to  substitute  in  the  calculation  for  100  cc.  the  equiva- 
lent amount  of  barium  hydroxide  used.  The  following  results 
were  obtained  by  the  coke  combustion  : 

Amount  taken.  Amount  found  by  titration. 

Gram.  Gram. 

0.0007  0.0075 

0.0256  0.0250 

0.0298  0.0290 

Two  grams  of  a  steel  containing  i  .07  percent,  carbon  were  now 
dissolved  in  150  cc.  of  a  50  percent,  solution  of  copper  potassium 
chloride  containing  5  percent,  of  concentrated  hydrochloric  acid. 
The  solution  was  kept  agitated  for  one  hour  at  a  gentle  heat  by 
means  of  a  stirring  apparatus.  It  was  then  allowed  to  remain 
quiet  for  several  hours  and  filtered  on  asbestos  in  a  platinum  boat, 
washing  with  dilute  hydrochloric  acid,  and  then  with  hot  water. 
The  carbonaceous  residue  was  burned  without  drying,  exactly 
as  the  coke  had  been.  The  results  were  i.n  and  1.12.  As 
these  results  are  decidedly  high  (the  results  using  potassium 
hydroxide  as  an  absorbent  being  1.072  percent.,  1.068  percent., 
i  .066  per  cent. ,  i  .070  per  cent. ) ,  several  combustions  were  made 
on  sugar  with  the  following  results  : 

Amount  taken.  Amount  found  by  titration. 

Gram.  Gram. 

0.0168  0.0164 

0.0162  0.0160 

0.0188  0.0185 

0.0170  0.0166 


Barium  Hydroxide  as  an  Absorbent.  in 

Another  series  of  combustions  on  standard  steels  gave  the  fol- 
lowing results,  the  barium  carbonate  precipitate  being  weighed 
after  ignition  as  well  as  the  solution  titrated  : 

Pound  by  Found  by  Found  by 

potassium  hydroxide.  titration.  weighing  barium  carbonate. 

Per  cent.  Per  cent.  Per  cent. 

0.489  0.484 

0.477  0.471 

0.325  0.310 

0.205  °-I93 


o.i  10  0.103 


It  will  be  seen  that  in  general  the  results  are  just  a  trifle  low 
on  carbon  from  other  sources  than  steel,  while  the  results  on 
steel  are  distinctly  higher  by  titration,  and  a  trifle  high  by 
weight. 

The  cause  of  the  errors  in  steel  was  traced  to  the  formation  of 
sulphurous  and  sulphuric  acid  from  the  carbonaceous  residue. 
To  obviate  this  error  a  solution  of  potassium  permanganate  in 
sulphuric  acid  was  interposed  between  the  combustion- tube  and 
the  barium  hydroxide.  With  this  form  of  apparatus  the  follow- 
ing results  were  obtained,  the  combustion  being  made  as  before, 
but  thirty  minutes  being  used  to  aspirate  : 

Found  by  Found  by  Found  by 

potassium  hydroxide.  titration.  weighing  barium  carbonate. 

Per  cent.  Per  cent.  Per  cent. 

f  0.603)  f  }  f  | 

\  0-599  \  \  0-60       \  \  0.595     \ 

(0.594)  (0.599    J  1 0.594    J 

0/177  /  0-473   \  /  0.470  \ 

°'477  10.470   /  \  0.465    I 

In  order  to  test  decisively  this  theory  of  the  causes  of  errors,  four 
more  determinations  were  made  using  ten  grams  in  each  of  a 
soft  steel  containing  0.075  per  cent,  carbon.  Two  of  these  com- 
bustions were  made  without  interposing  any  permanganate. 
The  results  were  : 


112  Barium  Hydroxide  as  an  Absorbent. 

Pound  by 

Found  by  titration.  weighing  barium  carbonate. 

Per  cent,  carbon.  Per  cent,  carbon. 

0.084  0.080 

0.084  0.079 

The  precipitates  of  barium  carbonate  were  now  dissolved  in 
hydrochloric  acid  and  filtered.  The  barium  sulphate  found  in  the 
first  case  weighed  0.0095  gram,  and  in  the  second  case  0.0075 
gram.  The  results  of  the  combustion  corrected  by  these  amounts 
give  respectively  0.075  per  cent,  and  0.074  per  cent. 

The  other  combustions,  interposing  permanganate,  gave  the 
following  results  : 

Found  by 

Found  by  titration.  weighing  barium  carbonate. 

Per  cent,  carbon.  Per  cent,  carbon. 

O.oSl  0.075 

0.080  0.075 

The  barium  carbonate  obtained  from  these  combustions  con- 
tained nothing  insoluble  in  hydrochloric  acid. 

In  conclusion  I  would  say  that  it  will  be  found  much  simpler  to 
burn  and  weigh  the  barium  carbonate  rather  than  to  titrate. 
The  high  combining  weight  of  barium  renders  it  possible  to 
weigh  extremely  small  amounts  of  carbon  when  present  as  bar- 
ium carbonate. 


AN  IMPROVEMENT  IN  THE    ZINC    REDUCTOR    FOR 

THE  DETERMINATION  OF  IRON  OR 

PHOSPHORUS.1 


BY  A.  G.  MCKENNA, 

Chemist  to  the  Sterling  Steel  Co.,  Demmler,  Pa. 

In  using  the  ordinary  form  of  reductor,  for  reducing  solutions 
of  iron  or  molybdic  acid  by  passing  through  a  column  of  finely 
granulated  zinc,  an  enormous  amount  of  zinc  is  consumed  in 
the  useless  reaction  between  the  free  acids  necessarily  present 
and  the  zinc,  while  a  comparatively  small  amount  takes  part 
in  the  reaction  by  which  the  iron  or  molybdic  acid  is  reduced. 

The  reactions  spoken  of  are 

Fe,(S04)8  +  Zn  =  2FeSO4  +  ZnSO4 
and  HaS04  +  2Zn  =  ZnSO4  +  H3. 

The  great  volume  of  hydrogen  set  free  by  the  second  reaction 
proves  very  annoying  during  the  operation  of  reduction,  and 
unless  an  extremely  powerful  suction  is  used,  the  liquid  can 
scarcely  be  drawn  through  the  zinc. 

As  it  is  known  that  zinc  which  has  been  amalgamated  is 
scarcely  attacked  by  weak  acid,  it  occurs  to  the  writer  to  try  the 
effect  of  amalgamating  the  granulated  zinc  before  using  it  in  the 
reductor. 

The  results  were  most  satisfactory.  The  reaction  between  the 
zinc  and  the  free  acid  was  almost  entirely  suppressed,  there  being 
scarcely  any  evolution  of  hydrogen  during  the  passing  of  the 
solution  through  the  zinc,  while  the  speed  of  the  reduction  was 
not  in  the  least  diminished. 

The  form  of  apparatus  used  is  shown  in  the  accompanying 
sketch.  In  preparing  it  for  use  a  small  plug  of  asbestos  is 
placed  in  the  bottom  of  the  tube  just  above  the  stop- cock.  A 
very  thin  layer  of  asbestos  will  be  found  sufficient.  It  should  be 
packed  loosely  so  that  a  steady  stream  of  water  will  run  through 
without  suction.  On  this  plug  about  200  grams  of  granulated 

1  Read  before  the  Chemical  Section  of  the  Engineer's  Society  of  Western  Pennsyl- 
vania, September  29,  1895. 


An  Improved  Zinc  Reductor.  115 

zinc  are  placed.  The  zinc  should  be  of  such  fineness  that  it  will 
pass  through  a  2o-mesh  sieve  but  not  through  a  3O-mesh.  Be- 
fore placing  it  in  the  reductor  it  is  thoroughly  amalgamated  by 
stirring  up  with  it,  in  a  small  beaker,  about  5  grams  of  mercury 
and  25  cc.  of  a  5  per  cent,  solution  of  sulphuric  acid.  The  zinc 
fills  the  straight  part  of  the  tube  about  two- thirds  full,  leaving  a 
sufficient  space  to  allow  the  addition  of  the  solution  which  is  to  be 
reduced.  After  the  zinc  is  in  position  the  tube  is  inserted  in  a 
filtration  flask  by  means  of  a  rubber  stopper  and  the  flask  con- 
nected with  the  suction.  The  zinc  is  washed  several  times  with 
a  5  per  cent,  solution  of  sulphuric  acid  and  is  then  ready  for  use. 

For  the  determination  of  iron  in  ores,  the  solution  of  the  ore 
after  the  excess  of  free  hydrochloric  acid  has  been  driven  off,  is 
diluted  and  filtered  into  a  5<x>-cc.  graduated  flask  and  diluted  to 
the  mark  with  water  after  cooling.  By  means  of  a  ico-cc. 
pipette,  100  cc.  are  transferred  to  a  small  beaker ;  5  cc.  of  a  50 
per  cent,  solution  of  sulphuric  acid  are  added  and  the  contents  of 
the  beaker  are  poured  into  the  reduction-tube,  the  glass  stop- 
cock being  opened  sufficiently  to  allow  the  solution  to  be  drawn 
through  by  a  gentle  suction.  There  will  be  scarcely  any  evolu- 
tion of  gas,  and  the  reduction  will  be  complete  even  though  the 
solution  runs  through  in  a  steady  stream.  The  tube  is  now 
washed  four  times  with  a  5  per  cent,  solution  of  sulphuric  acid, 
using  in  each  washing  about  50  cc.  of  solution.  It  is  important 
during  the  washing  to  avoid  drawing  successive  amounts  of  air 
through  the  zinc,  as,  for  reasons  stated  below,  this  will  lead  to 
low  results.  The  reduced  solution  is  now  titrated  by  standard- 
ized permanganate  and  a  duplicate  determination  is  made  on 
another  100  cc.  taken  from  the  graduated  flask.  These  dupli- 
cates should  agree  within  o.  i  per  cent. 

In  some  of  the  first  experiments  it  was  found  that  a  blank 
made  by  washing  five  successive  portions  of  5  percent,  sulphuric 
acid  through  the  tube,  allowing  a  current  of  air  to  be  drawn 
through  for  a  half  minute  between  the  washings,  required  an 
amount  of  permanganate  equivalent  to  0.003  gram  of  iron, 
although  no  iron  could  be  found  in  the  solution.  Blanks  made 
in  a  similar  way,  except  that  no  air  was  drawn  through  the 
tube,  were  colored  by  the  first  drop  of  permanganate.  Dupli- 


n6  An  Improved  Zinc  Reductor. 

cate  determinations  of  iron,  allowing  in  one  case  air  to  be  drawn 
through  and  in  the  other  not,  invariably  gave  results  from  0.2  to  0.3 
per  cent,  low,  in  the  cases  in  which  air  was  drawn  through  alter- 
nately with  the  sulphuric  acid.  The  facts  evidently  point  to 
the  formation  of  some  compound  which  oxidized  iron  and  was 
itself  oxidized  by  permanganate.  A  test  for  hydrogen  peroxide 
was  made  in  one  of  the  blanks  by  adding  a  few  crystals  of 
potassium  iodide  ;  on  standing  a  few  minutes  the  solution  began 
to  show  the  characteristic  color  of  free  iodine.  On  titration  with 
hyposulphite  it  was  found  that  0.0009  gram  hydrogen  peroxide 
was  present  in  the  blank.  This  amount  of  hydrogen  peroxide 
would  be  sufficient  to  oxidize  about  3  mgms.  of  iron.  In  regard 
to  the  amount  of  zinc  consumed  in  the  reduction  of  a  gram  of  63 
per  cent,  ore,  it  may  be  said  that  a  determination  of  the  zinc 
in  the  solution  after  complete  reduction,  gave  0.6  gram  of  zinc. 


ON  SOME  EVOLUTION  METHODS  FOR  SULPHUR  IN 
IRON  AND  STEEL. 

BY  W.  E.  GARRIGUES. 

By  utilizing  the  property  of  caustic  alkali  to  effectually  check 
a  current  of  hydrogen  sulphide,  followed  by  oxidation  after 
washing  out  the  single  test-tube  necessary  for  absorbing  the  gas, 
a  clean  and  inoffensive  solution  is  rapidly  prepared  for  final  pre- 
cipitation. 

The  evolution  is  conducted  exactly  as  for  the  iodine  titration 
except  that  10  grams  of  the  drillings  are  used  in  place  of  5. 
The  absorbing  liquid  is  10  per  cent,  caustic  soda,  and  65  cc. 
are  used  for  a  determination,  being  contained  in  a  single  test- 
tube,  to  the  bottom  of  which  the  delivery-tube  dips. 

50  cc.  of  water  are  poured  on  the  drillings  in  the  flask,  fol- 
lowed by  40  cc.  strong  hydrochloric  acid,  the  heat  of  the  reac- 
tion starting  a  brisk  evolution  of  gas  at  once.  After  com- 
plete solution  of  the  metal  and  boiling,  the  test-tube  is  rinsed 
into  a  beaker,  10  cc.  of  5  per  cent,  potassium  permanganate 
added  and  heated  to  boiling  ;  this  completes  the  oxidation. 
20  cc.  of  strong  hydrochloric  acid  are  next  poured  in,  followed 
by  15  cc.  saturated  oxalic  acid,  which  leaves  the  liquid  clear  and 
colorless.  Neutralize  the  ammonia,  just  clearing  with  hydro- 
chloric, and  precipitate  boiling  with  barium  chloride.  The  neu- 
tralization seems  to  be  necessary. 

Bromine  was  tried  before  permanganate,  but  gave  indication 
of  low  results.  The  possibility  of  correcting  this  error  seems  as- 
sured, but  bromine  is  sufficiently  unpleasant  to  let  alone  when 
something  else  will  answer  equally  as  well. 

The  figures  obtained  on  a  sample  of  steel  by  the  above  two 
methods  of  oxidation,  the  evolution  being  identical,  and  also  by 
the£  aqua  regia  method,  follow  : 

Potassium 

Aqua  regia.  Bromine.  permanganate. 

0.048  (  0.042  0.046 

0.049  1  °-°42  0-046 

2  •{  0.045  0.047 
/  0.047  0.048 

3  \  0.047  0.049 


i.  w«5 


n8  W.  E.  Garrigues. 

The  bromine  results  need  an  explanation. 

No.  i  was  oxidized  as  follows  :  Bromine  water  added  to  alka- 
line solution,  heated  to  boiling,  acidified,  and  bromine  boiled  off. 

No.  2  ditto,  except  alkaline  solution  boiled  one-half  hour 
after  addition  of  bromine. 

No.  3  ditto,  boiled  one  hour. 

The  one  objection  to  alkaline  oxidation  methods  is  the  prac- 
tical impossibility  of  obtaining  caustic  soda  free  from  sulphur  in 
some  form.  This  necessitates  subtracting  a  "  blank."  Some 
attempts  to  get  rid  of  the  sulphur  were  only  partly  successful  ; 
using  a  saturated  solution  as  a  basis  (obtained  in  exactly  the 
same  manner  as  was  described  for  getting  rid  of  carbonate  in  the 
first  part  of  this  paper),  reduced  the  blank  from  16  to  7.7  mgms. 
Adding  excess  of  barium  chloride  and  letting  stand  two  days 
reduced  it  to  only  12.1  rngms.  The  saturation  process  is  recom- 
mended, the  clear  liquid  being  diluted  to  15°  B.,  at  which  density 
it  contains  about  10  per  cent,  of  sodium  hydroxide. 

The  above-described  process  should  be  especially  advan- 
tageous in  the  accurate  analysis  of  pig-iron,  where  the  sulphur 
content  of  the  residue  is  to  be  determined.  In  that  case  there 
is  certainly  no  advantage  in  titrating  the  evolved  sulphur  with 
iodine  and  then  working  the  residue  gravimetrically  ;  instead 
the  two  are  combined  and  only  one  precipitation  made. 

As  to  the  iodine  titration  of  the  evolved  sulphur  arrested  by 
caustic  alkali,  some  experiments  warrant  the  conclusion  that  the 
method  is  a  strictly  empirical  one,  not  depending  upon  complete 
reactions  like  the  gravimetric  results. 

In  other  words  the  equation, 


in  which  253.7  iodine  are  equivalent  to  32  sulphur,  cannot  be 
assumed  as  a  basis  for  calculating  the  sulphur  value  of  an  iodine 
solution  of  known  strength.  The  results  thus  obtained,  when 
caustic  alkali  is  used,  are  always  too  low. 

A  solution  standardized  empirically,  /.  e.,  against  a  steel  of 
known  sulphur  content,  will  contain  less  iodine  than  one  stand- 
ardized by  calculating  from  its  oxidizing  power.  As  the  equa- 
tion before  stated  is  the  simplest  which  can  be  assumed  to  take 


Evolution  Methods  for  Sulphur.  119 

place  between  hydrogen  sulphide  and  iodine,  the  least  possible 
amount  of  iodine  as  compared  to  sulphur  entering  into  it,  the 
choice  of  two  explanations  remains  to  account  for  the  discrep- 
ancy :  ( i )  The  sulphur  is  not  all  evolved  from  the  steel  as  hy- 
drogen sulphide,  and  (2)  the  hydrogen  sulphide  is  partly  oxi- 
dized to  sulphuric  acid  in  the  alkaline  solution  during  evolu- 
tion. 

Kxperiment  No.  i  must  be  dropped  for  the  reason  that  when 
cadmium  chloride  is  used  the  whole  of  the  sulphur  evolved  pre- 
cipitates as  cadmium  sulphide,  and  again  becomes  hydrogen 
sulphide  on  acidifying,  as  shown  by  its  requiring  the  full  theo- 
retical quantity  of  iodine.  The  suggestion  of  partial  oxidation 
alone  remains  then,  to  account  for  the  shortage,  it  having  been 
proved  by  direct  experiment  that  no  hydrogen  sulphide  escapes 
during  titration.  The  means  of  doing  this  was  to  add  at  once 
an  excess  of  iodine  and  then  titrate  back  with  sodium  thiosul- 
phate. 

Following  are  results  obtained  on  the  same  sample  of  steel  men- 
tioned before,  and  shown  to  contain  about  0.048  per  cent,  sul- 
phur. The  absorption  in  caustic  alkali  was  carried  out  in 
precisely  the  same  manner  as  were  the  gravimetric  analyses 
previously  recorded : 

Caustic  soda  absorption.  Cadmium  chloride. 

Direct  with  iodine.    Back  with  sodium  thiosulphate. 

0.038  0.039  0.047 

0.039  °-°39  0-047 

0.042  8.041  0.049 

Similar  results  were  obtained  by  the  sodium  hydroxide  method 
on  standard  samples  kindly  furnished  by  Mr.  Camp  and  Mr. 
Handy,  all  of  which  were  sufficiently  concordant  to  have  been 
apparently  correct  had  any  one  of  the  samples  been  used  for 
standard  titrating  solution  instead  of  taking  its  theoretical  value. 
They  did  not,  however,  agree  among  themselves  quite  as  well 
as  either  the  gravimetric  results  or  those  obtained  volumetrically 
with  cadmium  chloride  as  an  absorbent,  the  series  above  given 
being  rather  better  than  the  average.  Both  absorbents  gave  a 
blank  titration  equivalent  to  0.002,  which  was  subtracted.  To 
sum  up  :  An  iodine  solution  cannot  be  used  indiscriminately  for 


I2O  Evolution  Methods  for  Sulphur. 

titrating  sulphur  evolved  into  caustic  alkali  and  cadmium  chlo- 
ride. The  former  requires  a  standard  steel  as  a  basis  of  calcu- 
lating, all  evolutions  being  made  as  nearly  as  possible  under  the 
same  conditions,  while  the  latter  can  be  interpreted  from  the 
theoretical  value  of  the  iodine  solution,  the  results  agreeing  more 
closely  among  themselves  and  being  obtained  with  less  attention 
to  minute  details.  Hence  the  cadmium  chloride  is  recommended. 


THE  DETERMINATION  OF  CHROMIUM.1 
BY  A.  G.  MCKKNNA, 

Chemist  to  the  Sterling  Steel  Co.,  Demmler,  Pa. 

The  following  method  for  the  determination  of  chromium  in 
steel  will  be  found  more  accurate  and  rapid  than  any  of  the  pub- 
lished methods  known  to  the  writer.  By  its  use  he  has  made 
several  thousand  chromium  determinations  with  uniformly  satis- 
factory results. 

The  process  is  based  upon  the  well-known  fact  that  chromic 
salts  can  be  oxidized  completely  to  chromic  acid  by  the  addition 
of  potassium  chlorate  to  a  concentrated  nitric  acid  solution,  and 
the  fact,  not  so  well  known,  that  the  presence  of  nitric  acid  does 
not  interfere  with  the  titration  of  chromic  acid  in  a  cold  solution 
by  means  of  ferrous  sulphate  and  permanganate. 

In  case  the  steel  contains  manganese  and  a  determination  of 
the  same  is  wanted  in  addition  to  the  determination  of  chromium, 
the  method  is  as  follows  :  Weigh  3  grams  of  steel  into  a  400- 
cc.  flask,  add  35  cc.  of  strong  hydrochloric  acid  and  boil  for  five 
or  ten  minutes,  which  will  be  found  sufficient  to  dissolve  com- 
pletely even  the  highest  chrome  steels.  When  most  of  the  hy- 
drochloric acid  is  boiled  off,  add  150  cc.  strong  nitric  acid,  and 
continue  the  boiling  until  no  more  brown  fumes  are  seen  at  the 
mouth  of  the  flask,  showing  that  the  hydrochloric  acid  has  all 
been  driven  off.  Remove  the  flask  from  the  flame  or  hot  plate, 
allow  to  cool  for  two  or  three  minutes,  and  then  add  10  grams  of 
potassium  chlorate  in  crystals.  It  is  best  to  allow  the  solution 
to  cool  slightly  before  adding  the  chlorate  in  order  to  diminish 
the  violence  of  the  effervescence  due  to  the  action  of  the  chlorate 
on  the  chromic  salts.  Replace  on  the  hot  plate  and  boil  down 
to  about  40  cc.  in  order  to  decompose  completely  the  potassium 
chlorate.  It  is  necessary  to  decompose  the  chlorate  completely 

1  Read  before  the  Chemical  Section  of  the  Engineers'  Society  of  Western  Pennsylva- 
nia, June  18,  1896. 


122  A.   G.  McKenna. 

or  results  will  be  from  o.i  to  0.2  per  cent,  high,  but  the  amount 
of  nitric  acid  left  in  the  solution  is  not  important.  At  this  stage 
the  chromium  will  all  be  in  the  solution  in  the  form  of  chromic 
acid.  The  manganese  will  be  precipitated  as  dioxide  and  gen- 
erally some  crystals  of  potassium  nitrate  arising  from  the  decom- 
position of  the  chlorate  will  have  separated  out.  Filter  off  the 
manganese  dioxide  on  an  asbestos  plug,  washing  the  precipitate 
three  times  with  cold  water.  Transfer  the  asbestos  and  the 
manganese  dioxide  to  the  flask,  in  which  the  original  precipita- 
tion was  made,  titrate  with  ferrous  sulphate  and  permanganate, 
according  to  Williams'  well-known  modification  of  Ford's 
method. 

Make  the  filtrate  from  the  manganese  dioxide  which  contains 
all  the  chromic  acid  in  a  nitric  acid  solution  up  to  about 
500  cc.  with  cold  water,  and  add  standardized  ferrous  sulphate 
solution  in  slight  excess  indicated  by  the  disappearance  of  the 
yellow  color  of  the  chromic  acid  and  the  appearance  of  the  clear 
green  color  of  chromic  nitrate  ;  then  add  standardized  perman- 
ganate to  oxidize  the  excess  of  ferrous  sulphate  used,  the  end- 
point  being  the  well-known  faint  pink  color. 

The  standard  ferrous  sulphate  is  made  by  dissolving  iron  wire 
of  known  purity  in  an  excess  of  dilute  sulphuric  acid,  diluting 
with  water  until  i  cc.  contains  0.003223  gram  of  iron  in  the  fer- 
rous condition. 

The  permanganate  solution  is  made  by  dissolving  1.8 18  grams 
of  pure  potassium  permanganate  in  a  liter  of  water ;  i  cc.  of 
the  permanganate  solution  will  then  oxidize  exactly  i  cc.  of  the 
ferrous  sulphate  solution,  and  the  number  of  cubic  centimeters 
of  ferrous  sulphate  used  to  reduce  the  chromic  acid  minus  the 
cubic  centimeters  of  permanganate  necessary  to  oxidize  the 
excess  of  ferrous  sulphate,  will  give  the  amount  of  chromium 
present  in  milligrams. 

For  example,  to  3  grams  of  steel  treated  as  above,  35  cc.  of 
the  ferrous  sulphate  are  added  to  reduce  the  chromic  acid  and 
then  5  cc.  of  permanganate  solution  are  found  necessary  to  pro- 
duce a  permanent  pink  ;  hence  3  grams  of  this  steel  contain  0.03 
gram  of  chromium  or  i  per  cent.  If  these  same  solutions  are 
used  for  the  titration  of  the  manganese  dioxide  by  the  Williams' 


The  Determination  of  Chromium.  123 

method,  each  cubic  centimeter  of  ferrous  sulphate  used  in  ex- 
cess of  the  cubic  centimeters  of  permanganate  used  in  the  back 
litration  equals  0.001418  gram  manganese. 

In  case  the  determination  of  manganese  is  not  required  and  it 
is  desired  to  avoid  the  filtration  from  the  manganese  dioxide,  the 
method  may  be  modified  by  diluting  the  solution  after  it  has 
been  boiled  down  to  40  cc.  by  the  addition  of  100  cc.  of  water 
and  a  few  drops  of  hydrochloric  acid,  which  will  at  once  dissolve 
the  manganese  dioxide  without  action  on  the  chromic  acid. 
The  solution  then  must  be  boiled  for  a  few  minutes  to  remove 
the  chlorine  set  free  by  the  reduction  of  the  manganese  dioxide, 
after  which  it  may  be  cooled  and  titrated  as  above. 

In  very  many  chrome  steels  the  amount  of  manganese  is  so 
inappreciable  in  comparison  with  the  chromium  that  for  practi- 
cal results  it  is  not  necessary  to  remove  the  manganese  dioxide 
either  by  filtration  or  solution  in  hydrochloric  acid  but  the  solu- 
tion may  be  diluted  after  the  evaporation  to  40  cc.  and  titrated 
at  once.  Of  course,  in  high  chrome  steels  it  is  not  necessary  to 
take  more  than  a  gram  for  the  analysis. 

For  the  determination  of  chromium  in  ores,  slags,  and  ferro- 
chromes,  beyond  a  doubt  the  best  method  of  decomposition  is 
by  fusion  with  sodium  peroxide  in  a  nickel  crucible,  which 
brings  about  complete  decomposition  in  two  or  three  minutes,  if 
the  sample  is  at  all  finely  ground. 

Duplicate  determinations  on  ores,  slags,  and  ferro- chromes, 
made  by  the  solution  of  the  sodium  peroxide  fusions  in  nitric 
acid  and  oxidation  by  potassium  chlorate,  gave  on  titration 
results  equivalent  to  those  obtained  by  the  usual  inethed  of  acidi- 
fying with  sulphuric  acid,  after  decomposing  the  excess  of  perox- 
ide by  boiling  in  a  water  solution.  Consequently  there  would 
be  no  advantage  in  the  chlorate  method  for  these  over  the  usual 
method,  except  that,  by  obtaining  a  clear  solution  of  fusion  in 
the  nitric  acid  preliminary  to  oxidation  with  chlorate,  all  danger 
from  incomplete  decomposition  leading  to  the  presence  of  parti- 
cles of  metal,  which  might  reduce  some  chromic  acid  on  the  ad- 
dition of  sulphuric  acid,  is  avoided. 

However,  in  the  writer's  experience,  the  decomposition  has 
always  been  complete. 


NOTES  ON  THE  ANALYSIS  OF   MILL  AND  PUDDLE 

CINDERS. 


BY  Jos.  M.  WILSON. 


Mill  cinder  is  used  in  our  furnace  as  part  of  the  burden  and  is 
almost  wholly  brought  in  car-load  lots.  As  the  railroad  people 
are  constantly  pushing  us  for  prompt  unloading,  methods  for 
rapid  determination  of  the  constituent  elements  of  these  cinders 
are  important.  Formerly  we  were  required  to  report  the  iron 
and  insoluble  matter  at  once  and  later  the  silica.  At  present  iron 
and  phosphorus  are  also  required  and  occasionally  manganese. 
Our  methods  are  as  follows  : 

IRON. 

Weigh  out  0.25  and  0.5  gram  into  lipless  beakers,  mois- 
ten with  10-15  cc-  water,  making  certain  that  the  mass  is 
well  broken  up,  add  quickly  20  cc.  concentrated  hydrochloric 
acid,  cover,  boil  gently  for  twenty  minutes  (or  let  digest  upon  a 
steam-table  one  hour,  then  bring  to  a  good  boil),  add  stannous 
chloride  solution,  from  a  pipette,  till  the  liquid  is  colorless,  boil 
two  minutes,  remove  to  the  steam- table  and  allow  to  settle.  The 
supernatant  liquid  must  be  colorless.  The  residue  will  vary 
from  light  gray  to  black  according  to  the  amount  of  powdered 
coke  present. 

Wash  into  a  No.  5  or  6  beaker,  rinse  a  small  beaker  thoroughly 
with  cold  water,  taking  care  to  remove  all  the  insoluble  matter. 
Make  the  volume  300  cc.,  stir  well,  add  30-40  cc.  mercuric  chlo- 
ride solution,  all  at  once,  stir,  run  in  potassium  dichromate  until 

4  drops  give  no  blue  coloration  with  a  drop  of  ferricyanide  indi- 
cator in  one-half  minute. 

Solutions  Used. — Potassium  dichromate,  4.9  grams  of  the  salt 
in  i  liter  of  water,  i  cc.  =  0.005  gram  iron.  Stannous  chloride, 
loo  grams  in  i  liter  hydrochloric  acid  ( i  :  i ) .  Mercuric  chloride, 
50  grams  in  i  liter  of  water.  Ferricyanide  indicator,  5  cc.  of  a 

5  per  cent,  solution  in  40  cc.  water. 


Analysis  of  Mill  and  Puddle  Cinders.  125 

INSOLUBLE    MATTER   AND    SILICA. 

Weigh  i  gram  into  a  5-inch  Royal  Meissen  dish,  stir  up 
with  20  cc.  water,  add  20  cc.  concentrated  nitric  acid,  stir  well, 
cover,  evaporate  to  dry  ness,  and  ignite  till  all  acid  smell 
is  gone.  Cool,  add  locc.  concentrated  hydrochloric  acid,  evapo- 
rate to  dryness,  ignite,  cool,  add  25  cc.  hydrochloric  acid,  evap- 
orate to  10  cc. ,  add  30  cc.  water,  and  heat  to  boiling.  Filter  through 
a  9-cm.  filter,  wash  with  hot  hydrochloric  acid  (i  :  i)  and  with 
cold  water  twice,  ignite,  cool,  and  weigh  insoluble  matter. 
Fuse  "insoluble"  with  six  to  eight  times  its  weight  of  so- 
dium carbonate,  dissolve  the  fusion  in  water,  acidify  with 
hydrochloric  acid,  evaporate  to  dryness,  ignite,  cool,  add 
10  cc.  concentrated  hydrochloric  acid,  dry,  and  ignite  to  render 
silica  entirely  insoluble  and  granular.  Cool,  add  25  cc.  hydro- 
chloric acid,  evaporate  to  one-half,  add  30  to  40  cc.  water,  heat  to 
boiling,  filter  on  a  9-cm.  filter,  wash  twice  with  hot  water, 
filling  the  filter  each  time  to  remove  salts,  then  with  hot  hy- 
drochloric acid  (i  :  i),  and  with  cold  water  twice,  then  four  to 
six  times  with  hot  water,  ignite,  cool,  and  weigh ;  or  moisten  insol- 
uble matter  with  water,  add  hydrofluoric  acid  till  a  clear  solution 
is  obtained,  then  5  or  6  drops  of  sulphuric  acid  (i  :  3),  evapo- 
rate, dry,  ignite  on  hot  plate  till  no  more  fumes  of  sulphur  tri- 
oxide  come  off,  then  heat  to  redness,  cool,  and  weigh.  L,oss  = 


SiO2. 


MANGANESE. 


This  is  determined  by  precipitation  with  potassium  chlo- 
rate, purification  of  the  manganese  dioxide  precipitate,  and  final 
weighings  as  Mn2P2O7,  by  the  acetate  method  or  by  color. 

PHOSPHORUS. 

Having  found  phosphorus  in  our  pig  metal  and  being  un- 
able to  determine  its  source  we  sought  it  in  ore,  flux,  and 
fuel,  but  not  finding  it  in  either  we  were  compelled  to  turn 
to  the  mill  cinder.  Up  to  this  time  we,  like  many  others,  sup- 
posed that  all  the  phosphorus  was  "  soluble"  inasmuch  as  mill 
cinders  are  easily  decomposable  silicates,  but  as  we  could  not 
locate  the  trouble  elsewhere  we  turned  our  attention  to  the  resi- 


126  Jos.  M.    Wilson, 

dues  which  we  fused  and  treated  for  phosphorus  ;  the  results 
took  us  completely  by  surprise,  for  we  found  that  no  matter 
what  the  total  amount  of  phosphorus  in  the  cinder  the  insoluble 
residue  invariably  carried  between  0.03  per  cent,  and 0.04  per  cent. 

As  the  fusion  of  the  residue  and  its  subsequent  treatment  took 
more  time  and  attention  than  we  could  give  it,  we  had  to  devise 
a  method  by  which  we  could  obtain  results  rapidly.  After  some 
experimenting  we  settled  on  the  following  scheme  :  Weigh  5 
grams  substance  into  a  platinum  dish,  stir  up  with  30  cc.  water, 
add  30  cc.  hydrofluoric  acid,  and  30  cc.  hydrochloric  acid.  Cover 
with  platinum  foil  supported  by  a  platinum  triangle,  evaporate  to 
dryness  over  an  Argand  burner  turned  low,  add  20  cc.  "hydrochloric 
acid,  evaporate  again  to  get  rid  of  hydrofluoric  acid,  add  30  cc. 
hydrochloric  acid,  evaporate  one-half,  and  wash  into  a  No.  3 
beaker.  Evaporate  to  a  sirup,  add  50  cc.  nitric  acid,  evaporate 
till  no  more  brown  fumes  come  off  and  liquid  is  sirupy,  add  30  cc. 
water,  and  heat  to  boiling.  Filter  through  a  y-cm.  filter  into  a 
i6-oz.  flask,  wash  filter  twice  with  cold  water,  and  once  with  hot 
nitric  acid  (sp.  gr.  1.20),  dropping  acid  from  a  pipette  on  the 
side  of  the  funnel  just  above  the  top  of  the  filter  ;  wash  acid  out 
of  filter.  Filter  retains  the  coke. 

Boil  filtrate,  add  potassium  permanganate  (12^  grams  to  i 
liter  of  water)  till  a  brown  precipitate  of  manganese  dioxide  sep- 
arates and  remains.  20  to  100  cc.  will  be  required,  according  to 
the  amount  of  carbonaceous  matter  dissolved  and  the  complete- 
ness with  which  hydrochloric  acid  has  been  driven  off  by  the 
nitric  acid  used  in  the  last  evaporation.  Reduce  the  manganese 
dioxide  with  ferrous  sulphate  (free  from  phosphorus) .  After  reduc- 
tion is  complete,  boil  ten  minutes,  cool,  and  add  strong  ammonia 
till  the  ferric  hydroxide  makes  a  thick  mud.  Redissolve  in  strong 
nitric  acid  to  clear  amber-colored  liquid,  and  insert  a  thermometer. 
When  temperature  is  88°  C.  pour  in  100  cc.  molybdate  solution. 
(Wood's  1 8  88  formula),  shake  five  minutes,  let  settle,  filter  off  yel- 
low precipitate,  wash  with  2  per  cent,  nitric  acid  (or  Dudley's  acid 
ammonium  sulphate)  five  times.  Remove  acid  by  five  washings 
with  potassium  nitrate  ( i :  1000) ,  and  determine  phosphorus  by  any 
convenient  method  :  (i)  weigh  yellow  precipitate,  (2)  titrate  the 
reduced  molybdic  acid  with  potassium  permanganate,  (3)  titrate 


Analysis  of  Mill  and  Puddle  Cinders.  127 

back  the  excess  of  standard  sodium  hydroxide,  etc.,  etc.  A  de- 
termination by  this  method  can  be  made  in  six  hours  without 
hurrying  the  evaporations  with  hydrofluoric  acid  and  hydro- 
chloric acid. 

The  following  method  has  been  used  when  not  in  a  hurry  :  5 
grams  in  a  5-inch  deep  dish  are  moistened  with  20  cc.  of  water,  and 
80  cc.  concentrated  nitric  acid.  Hydrochloric  acid  gelatinizes 
the  silica,  which  encloses  particles  of  undissolved  slag  and  is 
very  troublesome  to  handle.  Evaporate  to  dry  ness,  ignite  till 
no  more  acid  fumes  are  perceptible,  cool,  moisten  with  20  cc. 
hydrochloric  acid,  take  up  in  50  cc.  water,  filter,  wash  with  hot 
hydrochloric  acid  (i  :  i),  and  with  cold  water  till  free  from  iron. 
Ignite,  fuse  with  five  to  six  times  its  weight  of  sodium  carbon- 
ate, dissolve  in  hot,  dilute  nitric  acid,  evaporate  to  dryness, 
ignite  till  free  from  acid  fumes,  cool,  moisten  with  hydrochloric 
acid,  dry,  ignite  again,  cool,  moisten  with  hydrochloric  acid, 
take  up  with  water,  filter,  and  boil  filtrate.  Add  slight  excess 
of  ammonium  hydroxide,  boil  two  minutes,  filter,  wash  precipi- 
tate three  times  with  hot  water,  then  wash  into  a  beaker  contain- 
ing the  original  acid  solution,  and  boil  to  a  sirupy  consistency. 
Add  40  cc.  concentrated  nitric  acid,  boil  down  to  a  sirup,  add  25 
cc.  water,  heat  to  boiling,  filter  through  a  y-cm.  filter  into  a 
i6-oz.  flask,  wash  with  nitric  acid  and  water,  and  precipitate 
and  determine  phosphorus  as  above. 

The  precipitation  of  iron  and  aluminum  phosphate  from  a  solu- 
tion of  fusion  freed  from  silica,  serves  to  get  rid  of  the  great  ex- 
cess of  alkaline  salts  and  leaves  the  phosphorus  in  better  condi- 
tion for  precipitation. 

As  stated  above,  nitric  acid  is  a  better  solvent  for  mill  cinders 
than  hydrochloric  acid,  as  it  does  not  gelatinize  the  silica  and 
leaves  the  insoluble  matter  more  sandy  and  more  easily  filtered 
and  washed. 


I28  Analysts  of  Mill  and  Puddle   Cinders. 

Below  are  a  few  results  : 

Per  cent. 

Car.  No.    405,  Soluble  phosphorus 0.045 

"       "       493,         "  "  al3° 

«       «     3354,         ' '  ' '  0.800 

"       "     3354,  phosphorus  by  solution  in  nitric  acid  and 

fusion  of  residue 0.830 

"       "    4818,  Insoluble  phosphorus O-035 

"       "      537,         "  "  °'°38 

"       "       405,  Phosphorus  by  method  above 0.080 

"       "      493,  "  "        M  "       °'I65 

"       "     3354,  "  "         "  "       °'825 

"       "    4818,  Total  phosphorus 0.155 

«       «      577       "  "  0.060 

537, 


THE  COMPLETE  ANALYSIS  OF  CHROME  ORE.1 


BY  A.  G.  MCKENNA, 

Chemist  to  the  Sterling  Steel  Co.,  Demmler,  Pa. 

A  serious  objection  to  most  methods  of  chrome  ore  analysis 
has  been  the  difficulty  of  obtaining  complete  decomposition  of 
the  ore  without  prolonged  and  repeated  fusions  with  the  reagents 
generally  employed  for  that  purpose. 

By  fusing  the  ore  with  sodium  peroxide,  which  is  now  com- 
ing into  general  use  as  an  analytical  reagent,  any  chrome  ore  is 
completely  decomposed  in  a  few  minutes.  The  fusion  should 
not  be  made  in  platinum  as  the  peroxide  attacks  the  crucible 
strongly.  A  nickel  crucible  is  best  to  use,  although  it  is  also 
attacked  and  cannot  be  used  more  than  twenty  or  thirty  times. 
On  leaching  out  the  fusion  with  water  all  the  chromium  goes 
into  solution  as  sodium  chromate;  the  oxides  of  iron,  nickel,  and 
magnesium  remain  in  the  undissolved  residue.  The  following 
method  for  the  determination  of  silica,  oxide  of  iron  and  chro- 
mium, alumina,  lime,  and  magnesia  is  based  on  the  above-men- 
tioned facts. 

DETERMINATION  OF  OXIDES  OF  IRON  AND  CHROMIUM. 

0.5  gram  of  the  finely  ground  sample  which  has  been  dried  at 
1 00°  C.  for  one  hour  is  weighed  into  a  nickel  crucible  of  about 
20  cc.  capacity,  in  which  have  been  placed  3  or  4  grams  of 
sodium  peroxide ;  after  thoroughly  mixing  the  contents,  the 
crucible  is  held  over  a  Bunsen  burner  by  means  of  a  pair  of 
suitably  shaped  tongs,  until  fusion  begins.  The  mass  is  kept  in 
a  liquid  condition  at  a  low  red  heat  for  about  one  minute, 
which  is  sufficient  to  insure  complete  decomposition  if  the  ore  is 
at  all  finely  ground.  After  allowing  the  crucible  to  cool  it  is 
placed  in  a  4OO-cc.  beaker  with  a  watch-glass  cover  and  hot 
water  added  until  the  crucible  is  covered. 

i  Read  before  the  Chemical  Section  of  the  Engineer's  Society  of  Western  Pennsyl- 
vania, March  18,  1897. 


130  A.  G.  McKenna. 

The  beaker  is  placed  on  a  hot  plate  for  a  few  minutes  until 
the  fusion  is  dissolved  ;  the  crucible  is  then  removed  by  means 
of  a  glass  rod  and  the  contents  of  the  beaker  allowed  to  settle  for 
a  few  minutes.  When  the  insoluble  matter  has  subsided  it  is 
collected  on  a  9-cm.  filter-paper,  the  filtrate  being  received  in  a 
half-liter  flask.  The  residue  on  the  paper  which  contains  all 
the  iron  is  ignited  in  a  platinum  crucible,  fused  with  2  or  3 
grams  of  potassium  bisulphate,  dissolved  in  dilute  sulphuric  acid 
(i  :  10),  reduced  by  filtration  through  amalgamated  zinc,  and 
titrated  in  the  usual  manner  with  standard  permanganate.  The 
result  is  calculated  to  ferrous  oxide. 

The  filtrate  in  the  half-liter  flask,  which  contains  all  the  chro- 
mium as  sodium  chromate  in  an  alkaline  solution,  is  boiled  for 
about  ten  minutes  in  order  to  insure  the  removal  of  all  peroxide 
which,  if  allowed  to  remain  until  the  solution  is  acidified,  would 
react  on  the  chromate,  reducing  it  to  the  sesquioxide. 

When  the  removal  of  the  peroxide  is  complete  the  solution  is 
allowed  to  cool  and  then  acidified  with  a  large  excess  of  dilute 
sulphuric  acid  ( i  14). 

The  solution  is  transferred  to  a  i -liter  beaker,  and  diluted  to 
about  800  cc.  with  cold  water.  To  this  solution  70  cc.  of  a 
ferrous  sulphate  solution,  containing  10  grams  of  iron  (in  the 
ferrous  condition)  to  the  liter,  are  added ;  this  is  sufficient  to  re- 
duce the  chromic  acid  corresponding  to  0.3167  gram  of  chromic 
sesquioxide.  The  excess  of  ferrous  sulphate  which  has  been 
added,  is  determined  by  back  titration  with  standard  perman- 
ganate solution,  of  which  i  cc.  is  equivalent  to  i  cc.  of  the 
ferrous  sulphate  solution.  Such  a  permanganate  contains  5.643 
grams  potassium  permanganate  to  the  liter.  The  difference 
between  the  cubic  centimeters  of  ferrous  sulphate  used  and  the 
cubic  centimeters  of  permanganate  used,  multiplied  by  0.905, 
gives  the  percentage  of  chromic  sesquioxide  in  the  ore. 

For  the  determination  of  silica,  alumina,  ferric  oxide,  chromic 
sesquioxide,  lime,  and  magnesia,  fuse  one-half  gram  of  ore  in  a 
nickel  crucible  as  before,  dissolve  in  about  50  cc.  hot  water  in  a 
covered  5-inch  porcelain  dish,  remove  crucible  and  acidify  with 
hydrochloric  acid,  evaporate  to  dry  ness,  take  up  in  dilute  hydro- 
chloric acid  (i  14),  filter,  ignite,  and  weigh  as  SiO2.  To  the 


The  Complete  Analysis  of  Chrome  Ore.  131 

filtrate  add  10  cc.  strong  hydrochloric  acid,  make  ammoniacal, 
pass  hydrogen  sulphide,  allow  to  settle,  filter  off  the  precipitated 
hydrates  of  chromium  and  aluminum  and  the  sulphides  of 
iron  and  nickel.  Dissolve  the  iron,  chromium,  and  aluminum  in 
dilute  hydrochloric  acid  and  reprecipitate  as  before  with  hydrogen 
sulphide  and  filter.  In  the  combined  filtrates  determine  lime  and 
magnesia  in  the  usual  manner. 

Redissolve  the  iron,  chromium,  and  aluminum  precipitates 
from  the  filter-paper  with  dilute  hydrochloric  acid,  oxidize  with 
a  few  drops  of  nitric  acid,  precipitate  with  ammonia,  filter,  wash 
free  from  chlorine,  ignite,  and  weigh  as  A12O8,  Cr2O3,  Fe2O3. 
From  this  weight  subtract  the  Cr2O3  +  Fe2O3,  calculated  from 
the  percentage  of  iron  and  chromium  found  in  previous  analysis, 
which  will  give  the  alumina. 


INDEX. 


Alumina  in  blast-furnace  slag,  determination  of  103 

Barium  hydroxide  as  an  absorbent  in  carbon  determinations 109 

Barrett,  J.  C 80 

Black  Diamond  Steel  Works  laboratory,  Pittsburg,  Pa 23 

Brinker,  F.  G 60 

Calcium  in  blast-furnace  slag,  determination  of 104 

Carnahan,  R.  B.,  Jr.,  see  Tonnele,  Theo. 

Camp,  J.  M 88,  101 

Carbon  in  steel,   determination  of,  8,   14,  20,  27,  45,  55,  78,  86,  97 ; 

Barium  hydroxide  in  carbon  determinations 109 

Carnegie  Steel  Co.  laboratory,  Homestead,  Pa I 

"            "       "                "          Lucy  Furnace,  Pittsburg,  Pa   21 

"  "       "  "          Edgar  Thomson  Furnace,  Braddock, 

Pa 50 

Duquesne,  Pa 88,  101 

Chrome  ore,  complete  analysis  of 129 

Chromium,  determination  of 121,  129 

Chromium  in  chrome  ore  and  ferro-chrome,  determination  of 44 

Cinders,  analysis  of  blast-furnace,  101;  analysis  of  mill  and  puddle  ..  124 

Clifton,  Warren  R 63 

Clinton  Iron  and  Steel  Co.  laboratory,  Pittsburg,  Pa    57 

Cobalt  in  steel,  determination  of 42 

Crabtree,  Frederick 12 

Dudley,  C.  B 70 

Ferro-silicon  and  silico-spiegel,  determination  of  silicon  in 37 

Garrigues,  W.  E 117 

Graphite  in  pig  iron,  determination  of 45 

Hainsworth  Steel  Co.,  Edith  Furnace  Dept.,  Allegheny,  Pa 47 

Harrison  A.  B 57 

Iron  in  iron  ores,  determination  of,  i,  12,  16,  21,  23,  47,  50,  57,  60,  63, 

72,  74,  80,  89 ;  improvement  in  zinc  reductor 113 

Iron  oxide  in  blast-furnace  slag,  determination  of 103 

Iron  oxide  in  chrome  ores  129 

Isabella  Furnace  Co.  laboratory,  Etna,  Pa 60 

Johnson,  Edward  S 23 

Johnston,  R.  G  47 

Junction  Iron  and  Steel  Co.  laboratory,  Steubensville,  O 16 

Lime  in  blast-furnace  slag,  determination  of 104 

Magnesia  in  blast-furnace  slag,  determination  of 105 

Manganese  in  blast-furnace  slag,  determination  of « 105 

Manganese  in  ores,  determination  of 

5,  13,  18,  25,  52,53,  57,61,  64,  6872,  75,82,  90 


Index.  133 

Manganese  in  pig  iron,  determination  of 

10,  14,  18,  20,  21,  27,  49,  55,  58,  61,  67,  73,  77,  85,  92 

Manganese  in  steel,  determination  of 

10,  15,  18,  33,  40,  56,  58,  67,  73,  79,  85,  92 

Mclntosh,  Hemphill  and  Co.  laboratory,  Pittsburg,  Pa  72 

McKenna,  A.  G 109,  113,  121,  129 

Miller,  Robert 21 

M'Kelvey,  J.  P 72 

Monongahela  Furnace  laboratory,  McKeesport,  Pa 12 

Murray,  C.  B 50 

Nickel  in  steel,  determination  of n,  41,  42,  56,  58,  69,  73,  79,  96 

Ohio  Steel  Co.  laboratory,  Youngstown,  O 80 

Oliver  and  Snyder  Steel  Works  laboratory,  Pittsburg,  Pa 36 

Pennsylvania  R.  R.  Co.  laboratory,  Altoona,  Pa 70 

Phosphorus  in  blast-furnace  slag,  determination  of 107 

Phosphorus  in  steel,  pig  iron,  and  ores,  determination  of,  3,  12,  14, 

15,  17,  20,  21,  24,  27,  32,  39,  48,  49,  51,  54,  56,  57,  58,  61,  63,  66,  72, 

73;74>  77>  78,  81,  84,  88,  89 ;  improvement  in  zinc  redactor 113 

Reductor,  improvement  in 1 13 

Rodgers,  S.  M 36 

Shenango  Valley  Steel  Co.  laboratory,  Newcastle,  Pa 63 

Silica  in  blast-furnace  slag,  determination  of  •  •  • 102 

Silica  in  ores  of  iron  and  manganese,  determination  of 

i,  12,  16,  21,  23,  47,  50,  57,  60,  63,  72,  74,  80 

Silicon  in  pig  iron  and  steel,  determination  of 

6,  13,  19,  21,  26,  36,  37,  49,  54,  57,  58,  61,  64,  72,  76,  83,  87,  94 

Slag,  analysis  of  blast-furnace 101 

Sulphur  in  blast-furnace  slag,  determination  of 106 

Sulphur  in  pig  iron  and  steel,  determination  of,  7,  14,  15,  19,  21,  30,  37, 

49>  54>  56,  58,  64,  65,  72,  73,  76,  78,  83,  94 ;    evolution  methods 

for 117 

Tonnele,  Theo.  and  R.  B.  Carnahan,  Jr 74 

Unger,  John  S i 

Wilson,  Joseph  M 16,  124 

W.  Dewes  Wood  Co.  laboratory,  McKeesport,  Pa  74 


ENGINEERING  CHEMISTRY: 

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QUANTITATIVE   CHEMICAL  ANALYSIS 

FOR  THE  USE  OF 

STUDENTS,  CHEMISTS  ™  ENGINEERS 

BY 

THOMAS  B.  STILLMAN,  M.Sc.,  Ph.D., 

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